CN113019398A - High-activity self-supporting OER electrocatalyst material and preparation method and application thereof - Google Patents
High-activity self-supporting OER electrocatalyst material and preparation method and application thereof Download PDFInfo
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- CN113019398A CN113019398A CN202110228794.7A CN202110228794A CN113019398A CN 113019398 A CN113019398 A CN 113019398A CN 202110228794 A CN202110228794 A CN 202110228794A CN 113019398 A CN113019398 A CN 113019398A
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 67
- 230000000694 effects Effects 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 176
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 56
- 239000000243 solution Substances 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000002131 composite material Substances 0.000 claims abstract description 50
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- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 33
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 22
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 12
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- 239000011593 sulfur Substances 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
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- 239000003054 catalyst Substances 0.000 claims abstract description 7
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- 239000002135 nanosheet Substances 0.000 claims description 18
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- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
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- 239000002245 particle Substances 0.000 claims description 7
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 7
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- 238000005486 sulfidation Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000005987 sulfurization reaction Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
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- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
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- 238000004458 analytical method Methods 0.000 description 1
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- 210000001320 hippocampus Anatomy 0.000 description 1
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- 229910052741 iridium Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
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- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 1
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B01J35/33—
-
- B01J35/56—
-
- 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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
-
- 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 provides a high-activity self-supporting OER electrocatalyst material and a preparation method and application thereof. The electrocatalyst material comprises a foamed nickel substrate and NiFe with a heterostructure grown in situ on the foamed nickel substrate2O4/Ni3S4/Ni(OH)2A material. The invention also provides a preparation method of the electrocatalyst material, which comprises the following steps: placing the pretreated foamed nickel in an iron source aqueous solution for hydrothermal reaction; after the reaction is finished, washing and drying to obtain NiFe2O4/Ni(OH)2a/NF composite; the obtained NiFe2O4/Ni(OH)2Placing the NF material in a sulfur source water solution for carrying out a vulcanization reaction; after the reaction is finished, washing and drying to obtain the catalyst. The invention relates to an in-situ growth method of NiFe on NF three-dimensional framework2O4/Ni3S4/Ni(OH)2Has excellent electrocatalytic performance.
Description
Technical Field
The invention relates to a high-activity self-supporting OER electro-catalyst material, a preparation method and application thereof, and belongs to the field of electro-catalyst materials.
Background
In the modern society, the excessive combustion of fossil fuels such as coal and charcoal causes serious energy crisis and environmental pollution. The discharge of a large amount of pollutants not only causes serious damage to the ecological environment, but also endangers the survival and development of human beings. Therefore, the development and utilization of clean renewable energy to gradually replace fossil fuels is a major trend in future energy development. The hydrogen energy is an ideal clean energy source by virtue of the advantages of high energy density, large combustion heat value, no pollution of products and the like. Compared with other hydrogen production modes (such as coke oven gas hydrogen production, methane reforming hydrogen production and the like), the hydrogen production by water splitting by electrocatalysis is more efficient, and the product does not produce secondary pollution, so the method is widely concerned by researchers. However, Oxygen Evolution Reaction (OER) is a half reaction occurring at the anode during water electrolysis, which is very slow due to the conversion of multiple intermediate states and the transfer of multiple electrons involved in the reaction process, and requires a higher overpotential to drive the catalytic process than Hydrogen Evolution Reaction (HER) at the cathode, so that the synthesis of an efficient OER electrocatalyst to reduce the overpotential required for water electrolysis is significant for the actual electrocatalytic water splitting.
At present, the oxides of the noble metals Ir and Ru remain the predominant OER electrocatalysts by virtue of their excellent catalytic activity. But the large-scale industrial production of the noble metal is limited due to the defects of limited reserves of the noble metal, high price, relatively poor stability and the like. Therefore, the preparation of the non-noble metal-based OER catalyst with both activity and stability is the key point for improving the efficiency of water electrolysis. As a typical non-noble metal-based catalyst material, the transition metal layered hydroxide has the advantages of simple synthesis process, low price, high catalytic activity and the like, and is an ideal electrocatalyst material. For example: chinese patent document CN112023946A provides a preparation method of a self-supporting nickel-iron layered double hydroxide sulfide electrocatalyst, which comprises the following steps: pretreating the original foam nickel to obtain purified foam nickel; dissolving nickel nitrate hexahydrate, ferric nitrate nonahydrate and urea in deionized water according to a preset proportion to obtain a mixed solution; adding foamed nickel into the mixed solution to perform a hydrothermal reaction to obtain NiFe LDH/NF; putting NiFe LDH/NF into thioacetamide solution to carry out secondary hydrothermal reaction to obtain NiFe LDH-Sx/NF; wherein x is any number from 1 to 8. However, the catalytic activity of the above materials is low, and further improvement is required.
At present, the insufficient exposure of active sites of transition metal layered hydroxides due to their stacking of layered structures, combined with the inherently poor electrical conductivity, limits their application in electrocatalysis. Although there are many corresponding studies to optimize them continuously, the preparation of high activity transition metal based layered OER electrocatalysts in a simple and economical manner remains to be explored further.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a high-activity self-supporting OER electrocatalyst material, and a preparation method and application thereof. The invention takes the foam nickel as a matrix material, and prepares the self-supporting OER electro-catalyst with high activity in situ through low-temperature hydrothermal reaction and subsequent vulcanization treatment, and the obtained OER electro-catalyst can drive the oxygen evolution reaction to occur under extremely low overpotential.
The technical scheme of the invention is as follows:
a high-activity self-supporting OER electro-catalyst material comprises a foam nickel matrix (NF) and NiFe with a heterostructure grown in situ on the foam nickel matrix (NF)2O4/Ni3S4/Ni(OH)2A material; the NiFe2O4/Ni3S4/Ni(OH)2The micro-morphology of the material is Ni (OH)2Nanosheet and NiFe2O4Nanoparticles of Ni (OH)2Nanosheet and NiFe2O4Ni grows in situ at the nano-particle connecting interface3S4And (3) nanoparticles.
Preferred according to the invention, said Ni (OH)2The thickness of the nano-sheet is 100-140nm, and the transverse length is 300-400 nm; the NiFe2O4Nano meterThe particle diameter of the particles is 30-40nm, Ni3S4The particle size of the nano-particles is 8-12 nm.
According to the invention, the preparation method of the high-activity self-supporting OER electrocatalyst material comprises the following steps:
(1) placing the pretreated foamed nickel in an iron source aqueous solution for hydrothermal reaction; after the reaction is finished, washing and drying to obtain NiFe2O4/Ni(OH)2a/NF composite;
(2) NiFe obtained in the step (1)2O4/Ni(OH)2Placing the/NF composite material in a sulfur source water solution for carrying out a vulcanization reaction; after the reaction is finished, washing and drying to obtain NiFe2O4/Ni3S4/Ni(OH)2the/NF composite material is the high-activity self-supporting OER electro-catalyst material.
According to the invention, the pretreatment step in step (1) is preferably: respectively carrying out ultrasonic treatment on the foamed nickel in 1mol/L HCl solution, deionized water and absolute ethyl alcohol for 20min in sequence, and drying in vacuum at the temperature of 30 ℃; and (4) pretreating to remove impurities on the surface of the foamed nickel.
Preferably, according to the invention, the thickness of the nickel foam in step (1) is 1-2 mm.
According to the invention, the iron source in the step (1) is Fe (NO)3)3·9H2And O, wherein the concentration of the iron source water solution is 0.015-0.02 mol/L.
According to the invention, the volume of the iron source aqueous solution in the step (1) is 60-80% of the capacity of the polytetrafluoroethylene lining; the aqueous iron source solution is not required to be submerged in the nickel foam.
According to the invention, the temperature of the hydrothermal reaction in the step (1) is preferably 110-130 ℃, and the hydrothermal reaction time is 8-10 h.
According to the invention, the washing in the step (1) is preferably 3-5 times by using deionized water, and the drying is preferably drying at 50-60 ℃ for 10-12 h.
According to the invention, the sulfur source in the step (2) is Na2S·9H2O, concentration of said aqueous solution of sulfur sourceThe degree is 0.005-0.01 mol/L.
According to the present invention, the aqueous solution of the sulfur source described in the step (2) is not submerged in NiFe2O4/Ni(OH)2a/NF composite material.
According to the invention, the temperature of the vulcanization reaction in the step (2) is preferably 70-90 ℃, and the time of the vulcanization reaction is preferably 4-5 h.
According to the invention, the washing in the step (2) is preferably 3-5 times by using deionized water, and the drying is preferably drying at 50-60 ℃ for 10-12 h.
According to the invention, the high-activity self-supporting OER electrocatalyst material is applied as an OER catalyst for an electrolytic water oxygen evolution reaction.
The invention has the following technical characteristics and beneficial effects:
1. the preparation method of the high-activity self-supporting OER electrocatalyst material is simple, low-price commercial foam Nickel (NF) is used as a matrix material, and Fe is used3+Auxiliary low-temperature hydrothermal reaction and sulfurization reaction to obtain stable and high-activity self-supporting OER electrocatalyst material; in the preparation method, the concentrations of the iron source solution and the sulfur source solution need to be controlled, the excessive concentration of the iron salt can cause excessive corrosion of the foamed nickel substrate and influence the stability of the electrode, the concentration is too low, and the generated NiFe2O4Fewer particles affect OER activity; the sulfuration degree can be controlled by controlling the concentration of the sulfur source solution, so that the electrocatalyst material with high catalytic activity is obtained, and the sulfuration degree is smaller or larger due to too low or too high concentration of the sulfur source solution, so that the catalytic activity of the obtained electrocatalyst material is lower. Meanwhile, the invention has the advantages of mild synthesis conditions, low energy consumption, simple process, low equipment requirement and low cost, and the obtained NiFe2O4/Ni3S4/Ni(OH)2the/NF composite material has excellent electrocatalytic performance.
2. The high-activity self-supporting OER electro-catalyst material obtained by the invention has multiple components and is NiFe grown in situ on a three-dimensional skeleton of foamed nickel2O4/Ni3S4/Ni(OH)2Has excellent electrocatalysisThe performance is mainly caused by the following reasons: firstly, NiFe grows in situ on the three-dimensional skeleton of the foamed nickel2O4/Ni3S4/Ni(OH)2The heterostructure of (3) enables the matrix to be tightly combined with the catalytic active material, and accelerates the charge transfer between the matrix and the active material; secondly, the micro-morphology of the electrocatalytic material is Ni (OH)2Nanosheet and NiFe2O4The nanoparticles are connected, so that the specific surface area of the material is increased, more active sites are exposed, and the mass transfer efficiency of the catalytic process is improved; and Ni (OH) after the vulcanization treatment2Nanosheet and NiFe2O4In-situ growth of Ni between nanoparticle interfaces3S4The contact area between the nano particles and the electrolyte is further increased, more active sites are exposed, ion migration and rapid gas release in the reaction process are facilitated, and the mass transfer efficiency is improved; third, in the vulcanization process, in the NiFe2O4/Ni(OH)2Ni producing connection at interface3S4Nanoparticles, further modulating the electronic structure of the active center, strengthening Ni (OH)2Nanosheet and NiFe2O4The cooperation of the nano-particle heterostructure improves the charge transfer at a heterogeneous interface, accelerates the transfer of electrons between an electrode and an active site, enhances the stability of the interface, and obviously reduces the overpotential in the reaction process; and the cooperation optimization of the self-supporting heterostructure and charge transmission realizes the remarkable improvement of the OER performance. Experiments prove that the catalyst material obtained by the invention can be used for electrolyzing water and oxygen in a 1mol/L KOH solution to achieve 10mA/cm only by an ultra-low overpotential of 120mV2Is superior to most of the OER electrocatalysts reported at present.
3. The invention selects cheap foam nickel with excellent conductivity and three-dimensional framework as the current collector and reaction raw material, the used raw material has larger content in the earth, wide source, large-scale production in industry and low cost; and the resulting NiFe2O4/Ni3S4/Ni(OH)2The material directly grows on the surface of the foamed nickel, the synthesized catalyst does not need to be attached to the surface of the supporting electrode, and the method is simpleThe process is simplified and the production cost is reduced. The method provides a new synthesis idea for reasonably designing the construction of the self-supporting transition metal layered hydroxide heterostructure and provides an effective way for simply synthesizing and preparing the high-activity OER electrocatalyst.
Drawings
FIG. 1 is a NiFe alloy prepared in example 12O4/Ni3S4/Ni(OH)2XRD pattern of the/NF composite material, wherein the abscissa is diffraction angle 2 theta and the ordinate is intensity.
FIG. 2 is a NiFe alloy prepared in example 12O4/Ni3S4/Ni(OH)2SEM image of/NF composite material.
FIG. 3 is a NiFe alloy prepared in example 12O4/Ni3S4/Ni(OH)2TEM image of/NF composite.
FIG. 4 is a NiFe alloy prepared in example 12O4/Ni3S4/Ni(OH)2EDS diagram of/NF composite material.
FIG. 5 is a NiFe alloy prepared in example 12O4/Ni3S4/Ni(OH)2Mapping spectrum of/NF composite material.
FIG. 6 is a NiFe prepared in example 12O4/Ni(OH)2XRD pattern of the/NF composite material, wherein the abscissa is diffraction angle 2 theta and the ordinate is intensity.
FIG. 7 is a NiFe prepared in example 12O4/Ni(OH)2SEM image of/NF composite material.
FIG. 8 is a NiFe alloy prepared in example 12O4/Ni3S4/Ni(OH)2Plots of polarization curves (LSV) for the/NF composite and the electrocatalyst materials prepared in comparative examples 1-3, where the abscissa is the potential and the ordinate is the current density.
FIG. 9 is a NiFe alloy prepared in example 12O4/Ni3S4/Ni(OH)2Electrochemical impedance plots of/NF composite materials and electrocatalyst materials prepared in comparative examples 1-3, wherein the abscissa is the real partImpedance, the ordinate is the imaginary impedance.
Fig. 10 is a graph of polarization curves (LSVs) of electrocatalyst materials prepared in examples 1-3 and comparative examples 4-5, with potential on the abscissa and current density on the ordinate.
Detailed Description
The present invention is described in further detail below with reference to specific examples, but the scope of the present invention is not limited thereto.
Reagents and instrumentation: all the reagents used in the invention are analytically pure, and all the reagents are purchased and directly used without further treatment.
Ferric nitrate nonahydrate (Fe (NO)3)3·9H2O), sodium sulfide nonahydrate (Na)2S·9H2O), potassium hydroxide (KOH), hydrochloric acid (HCl 36.0-38.0%), anhydrous ethanol is available in Chinese medicine;
nickel Foam (NF) was purchased from the Producer sales division of the Hippocampus force of Taiyuan and had a thickness of 1.5 mm.
Electrochemical testing: the electrochemical test adopts a Shanghai Hua CHI 660E electrochemical workstation, a three-electrode test system is used during the test, wherein the cut material is directly used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum sheet (1cm multiplied by 1cm) electrode is used as a counter electrode, an electrolyte is newly prepared 1mol/L KOH (pH 13.6), and the test data are all subjected to 90% IR compensation.
Example 1
A preparation method of a high-activity self-supporting OER electrocatalyst material comprises the following steps:
(1) cutting the foamed nickel into 2cm multiplied by 3cm, respectively ultrasonically cleaning the cut foamed nickel in 1mol/L HCl solution, deionized water and absolute ethyl alcohol for 20min to remove impurities such as oxides on the surface of the foamed nickel, and drying in vacuum at 30 ℃ for later use; 0.75mmol of Fe (NO) was added under stirring3)3·9H2Dissolving O in 40mL of deionized water to obtain Fe (NO)3)3The solution was transferred to a 50mL Teflon liner, after which the treated nickel foam was immersed in Fe (NO)3)3Transferring the liner to the solutionSealing the stainless steel reaction kettle; reacting for 8 hours in an electric heating constant temperature blast oven at the temperature of 120 ℃, and naturally cooling to room temperature; taking out the reaction kettle, washing the obtained product with deionized water for 5 times, and drying at 60 ℃ for 12h to obtain NiFe2O4/Ni(OH)2a/NF composite material.
(2) Under the stirring condition, 0.3mmol of Na2S·9H2O was dissolved in 40mL of deionized water and the resulting Na was added2Transferring the S solution into a 50mL polytetrafluoroethylene lining, and obtaining NiFe in the step (1)2O4/Ni(OH)2the/NF composite material is immersed in the Na2And (4) in the S solution, transferring the lining into a stainless steel reaction kettle, and sealing. Reacting for 5h in an electric heating constant temperature blast oven at the temperature of 80 ℃, naturally cooling to room temperature, finally taking out the reaction kettle, washing the obtained product with deionized water for 5 times, and drying for 12h at the temperature of 60 ℃ to obtain NiFe2O4/Ni3S4/Ni(OH)2the/NF composite material is the high-activity self-supporting OER electro-catalyst material.
NiFe prepared in this example2O4/Ni3S4/Ni(OH)2The method for applying the/NF composite material to the electrolysis of water and oxygen evolution of alkaline aqueous solution comprises the following specific steps:
the electrochemical performance test adopts a Shanghai Hua CHI 660E electrochemical workstation, a three-electrode test system is used during the test, the prepared electro-catalyst material is directly used as a working electrode, Ag/AgCl is used as a reference electrode, a platinum sheet (1cm multiplied by 1cm) electrode is used as a counter electrode, and a test solution is a newly prepared 1mol/L KOH solution (pH 13.6) to carry out the electrochemical water splitting test. All tests were performed with 90% IR compensation and all potentials were converted to reversible hydrogen potential.
NiFe prepared in this example2O4/Ni3S4/Ni(OH)2The XRD pattern of the/NF composite material is shown in figure 1, and as can be seen from figure 1, the obtained composite material has the composition of NF and Ni (OH)2、NiFe2O4And Ni3S4Four phases. The obtained NiFe2O4/Ni3S4/Ni(OH)2The SEM image of the/NF composite material is shown in FIG. 2, and it can be seen from FIG. 2 that the product mainly comprises nano-sheets and nano-particles, the transverse length of the nano-sheets is about 400nm, the thickness is 100-140nm, the size of the nano-particles has two size distributions, one is larger size about 30nm, the other is small particles around the nano-sheets, the size is about 10nm, and the characteristic can be correspondingly proved in the TEM image of FIG. 3. The specific surface area is increased by the unique combination of the nano sheets and the nano particles, so that the exposure of active sites is facilitated, the active sites can be fully contacted with electrolyte, and the reaction process is accelerated. And the EDS spectra of the corresponding elements are shown in figure 4, and the composition and content of the elements in the composite material can be known from the images. The obtained NiFe2O4/Ni3S4/Ni(OH)2The mapping spectrum of the/NF composite material is shown in FIG. 5, in which the distribution of various elements can be clearly seen, wherein the distribution of the element Ni and the element O is uniform and consistent, which is consistent with that of Ni (OH)2Nanosheet and NiFe2O4Both elements are present in the nanoparticles; the distribution of the elements Fe and S is relatively sparse, which is mainly the same as the Fe and S which are mainly present in the less abundant NiFe2O4Nanoparticles and Ni3S4The nanoparticles are associated and S is distributed so as to surround Fe closely, which further illustrates Ni3S4In-situ growth of nanoparticles in NiFe2O4And Ni (OH)2At the heterointerface of (a). NiFe in the present example2O4/Ni(OH)2The XRD pattern of the/NF composite material is shown in FIG. 6. in FIG. 6, only NF and Ni (OH) can be seen2、NiFe2O4Three phases, illustrating that the sulfidation treatment is to produce Ni3S4Is critical, and NiFe2O4/Ni(OH)2The SEM image of the/NF composite is shown in fig. 7, where only the nanosheets and the larger nanoparticles are present, and no smaller nanoparticles are present. The above analysis shows that the composition of the nanosheet is Ni (OH)2The chemical composition of the larger nanoparticles is NiFe2O4The chemical composition of the smaller nanoparticles is Ni3S4The above tests show that NiFe2O4/Ni3S4/Ni(OH)2Successful synthesis of/NF composite materials.
NiFe prepared in this example2O4/Ni3S4/Ni(OH)2The polarization curve (LSV) of the/NF composite material obtained in a 1mol/L KOH solution at a linear scan rate of 5mV/s is shown in FIG. 8. it can be seen from FIG. 8 that the electrocatalyst material prepared in this example reaches 10mA/cm2The current density of the material is only 120mV, and the current density is far better than that of comparative examples 1-3 and most reported OER electrocatalysts, which shows that the material has excellent OER catalytic performance. The electrochemical impedance plot of fig. 9 shows a lower impedance value and a lower reaction resistance compared to the control material, and the above electrochemical data all demonstrate that the material of example 1 has excellent OER catalytic activity.
Example 2
A preparation method of a high-activity self-supporting OER electrocatalyst material comprises the following steps:
(1) cutting the foamed nickel into 2cm multiplied by 3cm, respectively ultrasonically cleaning the cut foamed nickel in 1mol/L HCl solution, deionized water and absolute ethyl alcohol for 20min to remove impurities such as oxides on the surface of the foamed nickel, and drying in vacuum at 30 ℃ for later use; 0.75mmol of Fe (NO) was added under stirring3)3·9H2Dissolving O in 40mL of deionized water to obtain Fe (NO)3)3The solution was transferred to a 50mL Teflon liner, after which the treated nickel foam was immersed in the above-mentioned Fe (NO)3)3In the solution, transferring the lining into a stainless steel reaction kettle, and sealing; reacting for 8 hours in an electric heating constant temperature blast oven at the temperature of 120 ℃, and naturally cooling to room temperature; taking out the reaction kettle, washing the obtained product with deionized water for 5 times, and drying at 60 ℃ for 12h to obtain NiFe2O4/Ni(OH)2a/NF composite material.
(2) Under the stirring condition, 0.2mmol of Na2S·9H2O was dissolved in 40mL of deionized water and the resulting Na was added2Transferring the S solution to a 50mL polytetrafluoroethylene lining, and carrying out the step (1)Obtaining NiFe2O4/Ni(OH)2the/NF composite material is immersed in the Na2And (4) in the S solution, transferring the lining into a stainless steel reaction kettle, and sealing. Reacting for 5h in an electric heating constant temperature blast oven at the temperature of 80 ℃, naturally cooling to room temperature, finally taking out the reaction kettle, washing the obtained product with deionized water for 5 times, and drying for 12h at the temperature of 60 ℃ to obtain NiFe2O4/Ni3S4/Ni(OH)2the/NF composite material is the high-activity self-supporting OER electro-catalyst material.
The procedure for applying the electrocatalyst material prepared in this example to the electrolysis of aqueous alkaline solution to evolve oxygen is as described in example 1.
NiFe prepared in this example2O4/Ni3S4/Ni(OH)2The polarization curve (LSV) of the/NF composite material obtained in a 1mol/L KOH solution at a linear scan rate of 5mV/s is shown in FIG. 10. it can be seen from FIG. 10 that a current density of 10mA/cm is reached2An overpotential of 136mV is required.
Example 3
A preparation method of a high-activity self-supporting OER electrocatalyst material comprises the following steps:
(1) cutting the foamed nickel into 2cm multiplied by 3cm, respectively ultrasonically cleaning the cut foamed nickel in 1mol/L HCl solution, deionized water and absolute ethyl alcohol for 20min to remove impurities such as oxides on the surface of the foamed nickel, and drying in vacuum at 30 ℃ for later use; 0.75mmol of Fe (NO) was added under stirring3)3·9H2Dissolving O in 40mL of deionized water to obtain Fe (NO)3)3The solution was transferred to a 50mL Teflon liner, after which the treated nickel foam was immersed in the above-mentioned Fe (NO)3)3In the solution, transferring the lining into a stainless steel reaction kettle, and sealing; reacting for 8 hours in an electric heating constant temperature blast oven at the temperature of 120 ℃, and naturally cooling to room temperature; taking out the reaction kettle, washing the obtained product with deionized water for 5 times, and drying at 60 ℃ for 12h to obtain NiFe2O4/Ni(OH)2a/NF composite material.
(2) Stirring, adding 0.4mmol ofNa2S·9H2O was dissolved in 40mL of deionized water and the resulting Na was added2Transferring the S solution into a 50mL polytetrafluoroethylene lining, and obtaining NiFe in the step (1)2O4/Ni(OH)2the/NF composite material is immersed in the Na2And (4) in the S solution, transferring the lining into a stainless steel reaction kettle, and sealing. Reacting for 5h in an electric heating constant temperature blast oven at the temperature of 80 ℃, naturally cooling to room temperature, finally taking out the reaction kettle, washing the obtained product with deionized water for 5 times, and drying for 12h at the temperature of 60 ℃ to obtain NiFe2O4/Ni3S4/Ni(OH)2the/NF composite material is the high-activity self-supporting OER electro-catalyst material.
The procedure for applying the electrocatalyst material prepared in this example to the electrolysis of aqueous alkaline solution to evolve oxygen is as described in example 1.
NiFe prepared in this example2O4/Ni3S4/Ni(OH)2The polarization curve (LSV) of the/NF composite material obtained in a 1mol/L KOH solution at a linear scan rate of 5mV/s is shown in FIG. 10. it can be seen from FIG. 10 that 10mA/cm is reached2The current density of (2) requires an overpotential of 175 mV.
Comparative example 1
This comparative example used nickel foam as the OER electrocatalyst directly.
The procedure of applying the electrocatalyst material of this comparative example to aqueous alkaline solutions to electrolyze water to evolve oxygen is as described in example 1.
The polarization curve (LSV) obtained at a linear scan rate of 5mV/s in a 1mol/L KOH solution for the OER electrocatalyst of the present comparative example is shown in FIG. 8. it can be seen from FIG. 8 that the electrocatalyst material of the present comparative example reaches 10mA/cm2The current density of the nickel foam material needs 347mV overpotential which is far higher than that of the example 1, the electrochemical impedance diagram is shown in FIG. 9, the impedance value is far higher than that of the example 1, and the above electrochemical data all prove that the OER catalytic activity of the nickel foam material is far lower than that of the material of the example 1.
Comparative example 2
A method for preparing a self-supporting OER electrocatalyst material, comprising the steps of:
cutting the foamed nickel into 2cm multiplied by 3cm, respectively ultrasonically cleaning the cut foamed nickel in 1mol/L HCl solution, deionized water and absolute ethyl alcohol for 20min to remove impurities such as oxides on the surface of the foamed nickel, and drying in vacuum at 30 ℃ for later use; 0.75mmol of Fe (NO) was added under stirring3)3·9H2Dissolving O in 40mL of deionized water to obtain Fe (NO)3)3The solution was transferred to a 50mL Teflon liner, after which the treated nickel foam was immersed in the above-mentioned Fe (NO)3)3Solution, transferring the inner liner into a stainless steel reaction kettle, and sealing; reacting for 8 hours in an electric heating constant temperature blast oven at the temperature of 120 ℃, and naturally cooling to room temperature. Taking out the reaction kettle, washing the obtained product with deionized water for 5 times, and drying at 60 ℃ for 12h to obtain NiFe2O4/Ni(OH)2the/NF composite material is the self-supporting OER electro-catalyst material.
The procedure of applying the electrocatalyst material of this comparative example to aqueous alkaline solutions to electrolyze water to evolve oxygen is as described in example 1.
NiFe prepared by the comparative example2O4/Ni(OH)2The polarization curve (LSV) obtained by the linear scanning speed of 5mV/s of the/NF composite material in 1mol/L KOH solution is shown in FIG. 8, and it can be seen from FIG. 8 that the electrocatalyst material prepared by the comparative example reaches 10mA/cm2The current density of (A) is 182mV higher than that of example 1; the electrochemical impedance plot is shown in FIG. 9, which shows a higher impedance value than that of example 1, and the electrochemical data above all demonstrate that NiFe2O4/Ni(OH)2The OER catalytic activity of the/NF composite material is lower than that of the example 1.
Comparative example 3
A method for preparing a self-supporting OER electrocatalyst material, comprising the steps of:
cutting the foamed nickel into a size of 2cm multiplied by 3cm, respectively ultrasonically cleaning the cut foamed nickel in 1mol/L HCl solution, deionized water and absolute ethyl alcohol for 20min to remove impurities such as oxides on the surface of the foamed nickel, and drying in vacuum at 30 ℃ for subsequent use; under the stirring condition, 0.3mmol of Na2S·9H2O was dissolved in 40mL of deionized water and the resulting Na was added2The S solution was transferred to a 50mL Teflon liner and the treated nickel foam was immersed in Na as described above2And (4) in the S solution, transferring the lining into a stainless steel reaction kettle, and sealing. And (3) reacting for 5h in an electric heating constant-temperature air blast oven at the temperature of 80 ℃, naturally cooling to room temperature, finally taking out the reaction kettle, washing the obtained product with deionized water for 5 times, and drying at the temperature of 60 ℃ for 12h to obtain the self-supporting OER electrocatalyst material.
The procedure of applying the electrocatalyst material of this comparative example to aqueous alkaline solutions to electrolyze water to evolve oxygen is as described in example 1.
The plot of the polarization curve (LSV) obtained for the electrocatalyst material prepared in this comparative example at a linear scan rate of 5mV/s in 1mol/L KOH solution is shown in FIG. 8. it can be seen from FIG. 8 that the electrocatalyst material prepared in this comparative example reached 10mA/cm2The current density of the capacitor is 300mV of overpotential which is far higher than that of the capacitor in the embodiment 1; the electrochemical impedance diagram is shown in fig. 9, and the impedance value is much higher than that of example 1, and the above electrochemical data all prove that the OER catalytic activity of the electrocatalyst material prepared in comparative example 3 is much lower than that of the material of example 1.
Comparative example 4
A method for preparing a self-supporting OER electrocatalyst material, comprising the steps of:
(1) cutting the foamed nickel into 2cm multiplied by 3cm, respectively ultrasonically cleaning the cut foamed nickel in 1mol/L HCl solution, deionized water and absolute ethyl alcohol for 20min to remove impurities such as oxides on the surface of the foamed nickel, and drying in vacuum at 30 ℃ for later use; 0.75mmol of Fe (NO) was added under stirring3)3·9H2Dissolving O in 40mL of deionized water to obtain Fe (NO)3)3The solution was transferred to a 50mL Teflon liner, after which the treated nickel foam was immersed in the above-mentioned Fe (NO)3)3In the solution, transferring the lining into a stainless steel reaction kettle, and sealing; reacting for 8 hours in an electric heating constant temperature blast oven at the temperature of 120 ℃, and naturally cooling to room temperature. Taking out the reaction kettle, washing the obtained product with deionized water for 5 times, and drying at 60 ℃ for 12h to obtain NiFe2O4/Ni(OH)2a/NF composite material.
(2) Under the stirring condition, 0.1mmol of Na2S·9H2O was dissolved in 40mL of deionized water and the resulting Na was added2Transferring the S solution into a 50mL polytetrafluoroethylene lining, and obtaining NiFe in the step (1)2O4/Ni(OH)2the/NF composite material is immersed in the Na2And (4) in the S solution, transferring the lining into a stainless steel reaction kettle, and sealing. Reacting for 5h in an electric heating constant temperature blast oven at the temperature of 80 ℃, naturally cooling to room temperature, finally taking out the reaction kettle, washing the obtained product with deionized water for 5 times, and drying for 12h at the temperature of 60 ℃ to obtain NiFe2O4/Ni3S4/Ni(OH)2the/NF composite material is the high-activity self-supporting OER electro-catalyst material.
The procedure of applying the electrocatalyst material prepared in this comparative example to aqueous alkaline electrolysis for oxygen evolution is as described in example 1.
NiFe prepared by the comparative example2O4/Ni3S4/Ni(OH)2The polarization curve (LSV) of the/NF composite material obtained in a 1mol/L KOH solution at a linear scan rate of 5mV/s is shown in FIG. 10. it can be seen from FIG. 10 that a current density of 10mA/cm is reached2An overpotential of 190mV is required, which is higher than that of example 1.
Comparative example 5
A preparation method of a high-activity self-supporting OER electrocatalyst material comprises the following steps:
(1) cutting the foamed nickel into 2cm multiplied by 3cm, respectively ultrasonically cleaning the cut foamed nickel in 1mol/L HCl solution, deionized water and absolute ethyl alcohol for 20min to remove impurities such as oxides on the surface of the foamed nickel, and drying in vacuum at 30 ℃ for subsequent use; 0.75mmol of Fe (NO) was added under stirring3)3·9H2Dissolving O in 40mL of deionized water to obtain Fe (NO)3)3The solution was transferred to a 50mL Teflon liner, after which the treated nickel foam was immersed in the above-mentioned Fe (NO)3)3In the solution, transferring the lining into a stainless steel reaction kettle, and sealing; in electric heating constant temperature blastReacting for 8 hours in an oven at 120 ℃, and naturally cooling to room temperature; taking out the reaction kettle, washing the obtained product with deionized water for 5 times, and drying at 60 ℃ for 12h to obtain NiFe2O4/Ni(OH)2a/NF composite material.
(2) Under the stirring condition, 0.8mmol of Na2S·9H2O was dissolved in 40mL of deionized water and the resulting Na was added2Transferring the S solution into a 50mL polytetrafluoroethylene lining, and obtaining NiFe in the step (1)2O4/Ni(OH)2the/NF composite material is immersed in the Na2And (4) in the S solution, transferring the lining into a stainless steel reaction kettle, and sealing. Reacting for 5h in an electric heating constant temperature blast oven at the temperature of 80 ℃, naturally cooling to room temperature, finally taking out the reaction kettle, washing the obtained product with deionized water for 5 times, and drying for 12h at the temperature of 60 ℃ to obtain NiFe2O4/Ni3S4/Ni(OH)2the/NF composite material is the high-activity self-supporting OER electro-catalyst material.
The procedure of applying the electrocatalyst material prepared in this comparative example to aqueous alkaline electrolysis for oxygen evolution is as described in example 1.
NiFe prepared by the comparative example2O4/Ni3S4/Ni(OH)2The polarization curve (LSV) of the/NF composite material obtained in a 1mol/L KOH solution at a linear scan rate of 5mV/s is shown in FIG. 10. it can be seen from FIG. 10 that a current density of 10mA/cm is reached2An overpotential of 200mV is required, which is much higher than that of example 1.
From the above data, it can be seen that the high activity self-supported OER electrocatalyst according to the present invention shows excellent oxygen evolution activity mainly for several reasons: on one hand, the heterostructure array grows in situ on the three-dimensional foam nickel framework, so that the specific surface area can be increased, and more active sites can be exposed; the open nanosheet array can increase the contact with electrolyte, accelerate the reaction process, quickly transfer the generated gas and improve the mass transfer efficiency in the reaction process. On the other hand, sulfurization produces a new heterogeneous interface, so that the nanosheets Ni (OH)2And the active species NiFe2O4Is more closely contacted and improvedThe charge transmission at the heterojunction is facilitated, and the rapid transfer of electrons at the matrix and the active site is facilitated, so that the reaction overpotential is reduced, and the reaction rate of the OER is further improved.
Claims (10)
1. The high-activity self-supporting OER electro-catalyst material is characterized by comprising a foamed nickel substrate and NiFe with a heterostructure grown in situ on the foamed nickel substrate2O4/Ni3S4/Ni(OH)2A material; the NiFe2O4/Ni3S4/Ni(OH)2The micro-morphology of the material is Ni (OH)2Nanosheet and NiFe2O4Nanoparticles of Ni (OH)2Nanosheet and NiFe2O4Ni grows in situ at the nano-particle connecting interface3S4And (3) nanoparticles.
2. The high activity self-supporting OER electrocatalyst material according to claim 1, wherein the ni (oh)2The thickness of the nano-sheet is 100-140nm, and the transverse length is 300-400 nm; the NiFe2O4The particle diameter of the nano-particles is 30-40nm, Ni3S4The particle size of the nano-particles is 8-12 nm.
3. The method of preparing the high activity self-supporting OER electrocatalyst material according to claim 1, comprising the steps of:
(1) placing the pretreated foamed nickel in an iron source aqueous solution for hydrothermal reaction; after the reaction is finished, washing and drying to obtain NiFe2O4/Ni(OH)2a/NF composite;
(2) NiFe obtained in the step (1)2O4/Ni(OH)2Placing the/NF composite material in a sulfur source water solution for carrying out a vulcanization reaction; after the reaction is finished, washing and drying to obtain NiFe2O4/Ni3S4/Ni(OH)2the/NF composite material is the high-activity self-supporting OER electro-catalyst material.
4. The method of claim 3, wherein the pre-treating step in step (1) is: respectively carrying out ultrasonic treatment on the foamed nickel in 1mol/L HCl solution, deionized water and absolute ethyl alcohol for 20min, and drying in vacuum at the temperature of 30 ℃.
5. The method of claim 3, wherein the thickness of said nickel foam in step (1) is 1-2 mm; the iron source is Fe (NO)3)3·9H2And O, wherein the concentration of the iron source water solution is 0.015-0.02 mol/L.
6. The method for preparing high-activity self-supporting OER electrocatalyst material according to claim 3, wherein the temperature of the hydrothermal reaction in step (1) is 110-; the washing is carried out for 3-5 times by using deionized water, and the drying is carried out for 10-12h at 50-60 ℃.
7. The method of claim 3, wherein the sulfur source in step (2) is Na2S·9H2O, wherein the concentration of the sulfur source water solution is 0.005-0.01 mol/L.
8. The method of claim 3, wherein the temperature of the sulfidation reaction in step (2) is 70-90 ℃ and the sulfidation reaction time is 4-5 h.
9. The method of claim 3, wherein the washing in step (2) is performed 3-5 times with deionized water, and the drying is performed at 50-60 ℃ for 10-12 h.
10. Use of the high activity self-supporting OER electrocatalyst material according to any one of claims 1 to 2 as an OER catalyst for electrolytic water oxygen evolution reactions.
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