CN110791771B - Integrated transition metal oxygen evolution catalytic material and preparation method thereof - Google Patents

Abstract

The invention discloses an integrated transition metal oxygen evolution catalytic material and a preparation method thereof, and the prepared (Tm)_aNm_b)_xRm_yThe oxygen evolution catalytic material is composed of an alloy thin strip compounded by two layers of structures, wherein one layer is a nano porous layer of which the surface is doped with a transition metal oxide or hydroxide with high catalytic activity and a noble metal, and the other layer is a high-conductivity amorphous alloy matrix. The oxygen evolution catalytic material is directly in a (Tm) state with an amorphous nanocrystalline composite structure_aNm_b)_xRm_yThe alloy is a precursor, wherein Tm is one or more of Fe, Ni and Co, Nm is one or more of P, C, Si and B, and Rm is one or more of noble metals Ru, Rh, Os, Ir, Pt, Pd, Ag and Au. The method realizes the integrated preparation of the catalyst and the conductive carrier, and the obtained catalytic material can be directly used as a water electrolysis anode and has excellent oxygen evolution catalytic performance. The preparation method is convenient, simple and easy to control in process and suitable for large-scale production.

Description

Integrated transition metal oxygen evolution catalytic material and preparation method thereof

Technical Field

The invention relates to a catalytic material, in particular to an integrated transition metal oxygen evolution catalytic material and a preparation method thereof, belonging to the technical field of oxygen evolution electrocatalysis.

Background

Oxygen evolution reactions are one of the most common electrochemical reactions in the electrochemical industry. In research and actual production, it is always desirable for the water electrolysis anodic oxygen evolution reaction to have the anodic potential as low as possible at a certain current density, i.e. the anodic oxygen evolution material is required to have the oxygen evolution electrocatalytic activity as high as possible. The ease of the oxygen evolution reaction under certain electrolysis conditions depends mainly on the choice of anode material (electrocatalyst).

The traditional research on oxygen evolution catalytic materials mostly focuses on the powder state, so that the traditional research on the oxygen evolution catalytic materials is easy to agglomerate in the oxygen evolution reaction process, and the effective transmission of the quality is hindered; on the other hand, the catalysts are loaded on the collector plate, so that the series resistance of the electrodes is increased, and the energy consumption is increased. Practice proves that the anode oxygen evolution catalytic material with practical value has the characteristics of large specific surface area, low Tafel slope, low overpotential, high stability and the like.

Disclosure of Invention

The invention provides a design idea of catalyst-electrode integration; preparing a nano porous structure on the surface of a thin strip with an amorphous and nanocrystalline composite structure by using the corrosion resistance difference between amorphous and nanocrystalline, and introducing various transition metal (hydrogen) oxides with active chemical properties and noble metal substances with high catalytic activity on the surface to realize in-situ introduction of an active center on the surface of a high-conductivity thin strip; the material has self-supporting property, can be directly used as an oxygen evolution catalytic electrode, is applied to the field of oxygen evolution electrocatalysis, avoids the problem that a powder type catalyst is easy to agglomerate and deactivate, greatly reduces the series resistance between the catalyst and a conductive carrier, and has important application value. The component of the integrated transition metal oxygen evolution catalytic material is (Tm)_aNm_b)_xRm_yWherein (Tm)_aNm_b)_xRm_yThe atomic percentage of the dosage is that x + y is 100, x is more than or equal to 80 and less than or equal to 99.5; a + b is 1, and a is more than or equal to 0.75 and less than or equal to 0.95;

tm is one or more of Fe, Ni and Co;

nm is one or more than one of P, C, Si and B;

rm is one or more of noble metals Ru, Rh, Os, Ir, Pt, Pd, Ag and Au.

The invention also aims to provide a method for preparing the integrated transition metal oxygen evolution catalytic material, which comprises the following steps:

step one, preparing target components;

according to (Tm)_aNm_b)_xRm_yThe required elements are weighed in sequence, and the purity of each element is not lower than 99.9%; wherein:

tm is one or more of Fe, Ni and Co;

nm is one or more than one of P, C, Si and B;

rm is one or more of noble metals of Ru, Rh, Os, Ir, Pt, Pd, Ag and Au;

said (Tm)_aNm_b)_xRm_yThe atomic percentage of the dosage is that x + y is 100, x is more than or equal to 80 and less than or equal to 99.5; a + b is 1, and a is more than or equal to 0.75 and less than or equal to 0.95;

step two, preparing a master alloy;

step one is weighed to be good (Tm)_aNm_b)_xRm_yMixing the target components, putting into a vacuum arc melting furnace, setting melting parameters, and melting to obtain (Tm)_aNm_b)_xRm_yThe amorphous nanocrystalline master alloy ingot of (a);

smelting parameters are as follows: the smelting protective atmosphere is argon with the mass percentage of 99.999 percent; vacuum degree of 1X 10^-4～8×10^-3Pa; the smelting current is 30-200A; smelting for 1-20 min, and smelting for 1-10 times;

thirdly, preparing an amorphous nanocrystalline alloy thin strip by a melt spinning method;

(Tm) obtained in the second step_aNm_b)_xRm_yThe amorphous nano-crystalline master alloy is mechanically crushed into small blocks and then is preset in a quartz tube, and is put into a vacuum induction melting furnace of a rapid solidification device along with the quartz tube; setting alloy strip parameter, to (Tm)_aNm_b)_xRm_yAfter completely melting, spraying the molten mixture on a copper wheel rotating at a high speed to prepare a product with a thickness (Tm) of 0.05-200 mu m_aNm_b)_xRm_yAn alloy thin strip;

preparing alloy thin strip parameters: the width of an outlet at the bottom of the quartz tube is 1-6 mm, and the smelting protective atmosphere is argon with the mass percent of 99.0%; vacuum degree of 6X 10^-2～2×10^-1Pa; the coil induction current is 2-20A; the injection pressure is 0.01-0.1 MPa; the rotation linear speed of the copper wheel is 15-50 m/s;

selectively corroding to prepare a nano porous structure;

step 41, using conductive adhesive to connect the copper wire and the (Tm) prepared in step three_aNm_b)_xRm_yThe non-test ends of the thin alloy strip are fixedly connected and sealed with a non-conductive resin to expose (Tm)_aNm_b)_xRm_yAlloy thin stripThe free surface of (a);

step 42, converting (Tm)_aNm_b)_xRm_yThe free surface of the alloy thin strip is used as a working electrode, a graphite rod with the diameter of 3mm and the length of 100mm is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode;

43, performing corrosion treatment in an acidic corrosion medium with the concentration of 0.001-5 mol/L by adopting a three-electrode method to obtain the nano porous structure (Tm) with the surface_aNm_b)_xRm_yA base amorphous alloy ribbon;

the corrosion potential is 0V-0.5V (vs. SCE), the corrosion time is 5 min-60 min, and the corrosion temperature is 298K;

step five, cleaning treatment;

the surface prepared in the fourth step has a nano porous structure (Tm)_aNm_b)_xRm_yCleaning the base amorphous alloy thin strip for 3-5 times by using deionized water, and then cleaning for 3-5 times by using absolute ethyl alcohol; then placing the mixture into a vacuum drying oven, treating the mixture for 15-45 min at the drying temperature of 60-80 ℃, cooling the mixture to room temperature, and taking out the cooled mixture to obtain the nano-porous material (Tm) with the surface having nano-pores_aNm_b)_xRm_yIs an oxygen evolution catalyst material and has a thickness of 0.05 to 200 μm;

prepared (Tm)_aNm_b)_xRm_yThe oxygen evolution catalytic material is composed of an alloy thin strip compounded by two layers of structures, wherein one layer is a nano porous structure with the surface doped with transition metal oxides or hydroxides and noble metals, and the other layer is a high-conductivity amorphous alloy matrix.

The invention discloses a method for preparing an anode oxygen evolution electroplate of an integrated transition metal system oxygen evolution catalytic material, which is to prepare a nano-porous (Tm) electroplate in a three-electrode system_aNm_b)_xRm_yThe oxygen evolution catalyst material is used as an anode electrode. At 10mA/cm²The oxygen evolution geometric overpotential under the current density is 170-280 mV.

Compared with the prior art, the integrated transition metal oxygen evolution catalytic material has the advantages that:

firstly, the components of the integrated transition metal oxygen evolution catalytic material prepared by the invention are controllable, and the integrated transition metal oxygen evolution catalytic material is realized by adjusting the components of a precursor. One or more non-metal elements and transition metal elements with high catalytic activity are designed and added by utilizing the high solid solution of the amorphous alloy.

Tm can be used as a catalytic active component in the integrated transition metal oxygen evolution catalytic material prepared by the invention, Nm can improve the amorphous forming capability of a thin strip, Rm can be used as a high catalytic active element, and the cooperation of the three elements ensures that the material has low overpotential and low Tafel slope when being used as a water electrolysis anode material.

The thickness and the aperture size of the nano porous layer of the integrated transition metal oxygen evolution catalytic material prepared by the invention can be regulated and controlled, and can be realized by regulating the rotating speed of a copper wheel in the rapid solidification process and the corrosion potential in the constant potential corrosion process.

The integrated transition metal oxygen evolution catalytic material prepared by the invention is a continuous, tough and stable alloy thin strip with the thickness of 0.05-200 mu m.

The integrated transition metal oxygen evolution catalytic material prepared by the invention has the advantages that the existence of the surface nano porous structure increases a reaction channel at the solid-liquid interface of the water electrolysis anode, can be beneficial to the effective transmission of reactants and products in the oxygen evolution process, improves the oxygen evolution efficiency of the water electrolysis anode, and is at 10mA/cm²The oxygen evolution geometric overpotential under the current density is 170-280 mV.

Sixthly, the integrated transition metal oxygen evolution catalytic material prepared by the invention has the advantages that the transition metal oxide or hydroxide doped with nano-pores on the surface and the noble metal can be used as an active center, the intrinsic catalytic activity of the material is further increased, and the oxygen evolution overpotential and the Tafel slope are obviously reduced.

The integrated transition metal oxygen evolution catalytic material prepared by the invention has self-supporting property and can be directly used as a water electrolysis anode electrode, thereby shortening the process flow and providing convenient conditions for large-scale production. On one hand, the problem that the powder catalyst is easy to agglomerate and deactivate is effectively avoided, and on the other hand, the series resistance between the catalyst and the conductive carrier is greatly reduced.

The preparation method adopted by the invention is simple, has simple steps, convenient operation, easily controlled process parameters and cheap and easily obtained raw materials, is suitable for large-scale production, and has great application value in the field of hydrogen production by water electrolysis.

Drawings

FIG. 1 is an X-ray diffraction chart of a sample obtained in step three in example 1.

FIG. 2 is an X-ray diffraction chart of a sample obtained in step five in example 1.

FIG. 3 is an SEM picture of a sample prepared in step five of example 1.

FIG. 4 is an XPS picture of Ru3d of the sample prepared in step five in example 1.

FIG. 5 is an XPS picture of Co2p of the sample obtained in step five of example 1.

FIG. 6 is an XPS picture of Ni2p of the sample obtained in step five of example 1.

FIG. 7 is an XPS picture of O1s of a sample obtained in step five in example 1.

FIG. 8 is an XPS picture of P2P of the sample obtained in step five of example 1.

FIG. 9 is a TEM picture of a cross-section of a sample obtained through step five in example 1.

FIG. 9A is a sectional view showing the structure of a sample obtained in the fifth step in example 1.

FIG. 9B is a selected area electron diffraction pattern of the sample matrix prepared in step five of example 1.

FIG. 10 is a graph of the oxygen evolution catalysis of the sample prepared in step five in example 1.

FIG. 11 is a Tafel plot of the oxygen evolution catalyst prepared in step five in example 1.

FIG. 12 is a graph showing the stability of the oxygen evolution catalyst of the sample prepared in step five in example 1.

Detailed Description

The present invention will be described in further detail with reference to the accompanying drawings and examples.

The preparation method of the integrated transition metal oxygen evolution catalytic material comprises the following specific steps:

step one, preparing target components;

according to (Tm)_aNm_b)_xRm_yThe required elements are weighed in sequence, and the purity of each element is not lower than 99.9%; wherein:

tm is one or more of Fe, Ni and Co;

nm is one or more than one of P, C, Si and B;

rm is one or more of noble metals of Ru, Rh, Os, Ir, Pt, Pd, Ag and Au;

said (Tm)_aNm_b)_xRm_yThe atomic percentage of the dosage is that x + y is 100, x is more than or equal to 80 and less than or equal to 99.5; a + b is 1, and a is more than or equal to 0.75 and less than or equal to 0.95;

step two, preparing a master alloy;

step one is weighed to be good (Tm)_aNm_b)_xRm_yMixing the target components, putting into a vacuum arc melting furnace, setting melting parameters, and melting to obtain (Tm)_aNm_b)_xRm_yThe amorphous nanocrystalline master alloy ingot of (a);

smelting parameters are as follows: the smelting protective atmosphere is argon with the mass percentage of 99.999 percent; vacuum degree of 1X 10^-4～8×10^-3Pa; the smelting current is 30-200A; smelting for 1-20 min, and smelting for 1-10 times;

in the invention, for the alloy containing P element, the simple substance of P element and one or more simple substances of (Fe, Ni, Co) are mixed firstly, and then the mixture is smelted by a vacuum induction smelting furnace, wherein the smelting protective atmosphere is argon with the mass percent of 99.999 percent, and the vacuum degree is 3 multiplied by 10^-3Pa, smelting current of 80A for 6min to prepare a pre-alloy ingot; then putting the pre-alloy ingot and the rest elements into a vacuum arc melting furnace to be melted uniformly to obtain a master alloy ingot;

thirdly, preparing an amorphous nanocrystalline alloy thin strip by a melt spinning method;

(Tm) obtained in the second step_aNm_b)_xRm_yThe amorphous nano-crystalline master alloy is mechanically crushed into small pieces, is preset in a quartz tube and is then subjected to crushingPutting the quartz tube into a vacuum induction melting furnace of a rapid solidification device; setting alloy strip parameter, to (Tm)_aNm_b)_xRm_yAfter completely melting, spraying the molten mixture on a copper wheel rotating at a high speed to prepare a product with a thickness (Tm) of 0.05-200 mu m_aNm_b)_xRm_yAn alloy thin strip;

preparing alloy thin strip parameters: the width of an outlet at the bottom of the quartz tube is 1-6 mm, and the smelting protective atmosphere is argon with the mass percent of 99.0%; vacuum degree of 6X 10^-2～2×10^-1Pa; the coil induction current is 2-20A; the injection pressure is 0.01-0.1 MPa; the linear speed of the copper wheel is 15-50 m/s.

Selectively corroding to prepare a nano porous structure;

step 41, using conductive adhesive to connect the copper wire and the (Tm) prepared in step three_aNm_b)_xRm_yThe non-test ends of the thin alloy strip are fixedly connected and sealed with a non-conductive resin to expose (Tm)_aNm_b)_xRm_yA free surface of the alloy thin strip;

step 42, converting (Tm)_aNm_b)_xRm_yThe free surface of the alloy thin strip is used as a working electrode, a graphite rod with the diameter of 3mm and the length of 100mm is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode;

43, performing corrosion treatment in an acidic corrosion medium (one or more of sulfuric acid, hydrochloric acid and nitric acid, the concentration is 0.001-5 mol/L) by adopting a three-electrode method to obtain the (Tm) with the surface having the nano-porous structure_aNm_b)_xRm_yA base amorphous alloy ribbon;

the corrosion potential is 0V-0.5V (vs. SCE), the corrosion time is 5 min-60 min, and the corrosion temperature is 298K;

step five, cleaning treatment;

the surface prepared in the fourth step has a nano porous structure (Tm)_aNm_b)_xRm_yCleaning the base amorphous alloy thin strip for 3-5 times by using deionized water, and then cleaning for 3-5 times by using absolute ethyl alcohol; then put into a vacuum drying ovenTreating at 60-80 deg.c for 15-45 min, cooling to room temperature and taking out to obtain nanometer porous material (Tm)_aNm_b)_xRm_yIs an oxygen evolution catalytic material.

Prepared (Tm)_aNm_b)_xRm_yThe oxygen evolution catalytic material is composed of an alloy thin strip compounded by two layers of structures, wherein one layer is a nano porous structure with the surface doped with transition metal oxides or hydroxides and noble metals, and the other layer is a high-conductivity amorphous alloy matrix.

In the invention, the integrated preparation of the catalyst and the conductive carrier is realized through the steps from one to five to obtain (Tm)_aNm_b)_xRm_yThe oxygen evolution catalyst material can be directly used as a water electrolysis anode.

Oxygen evolution Performance test

The electrochemical experiment is carried out on a Princeton Applied Research Versa STAT 3 electrochemical workstation at 298K, a traditional three-electrode system is adopted, a graphite rod with the diameter of 3mm and the length of 100mm is used as an auxiliary electrode, a saturated calomel electrode is used as a reference electrode, and the prepared electrode has nano-porous (Tm) on the surface_aNm_b)_xRm_yThe oxygen evolution catalyst material is used as an anode electrode. In the invention, a copper wire is fixedly connected with the sample prepared in the fifth step by using conductive adhesive, the non-testing part is sealed by using non-conductive resin, the free surface of the alloy thin strip is exposed and used as an anode electrode for carrying out oxygen evolution performance test, the electrolyte is 1mol/L KOH solution, and the scanning speed of the potentiodynamic polarization curve is 2 mV/s.

The sample prepared by the method can be characterized by an X-ray diffractometer, a scanning electron microscope, a transmission electron microscope and an X-ray photoelectron spectrometer, and finally the oxygen evolution performance of the sample prepared by the method is tested on an electrochemical workstation connected with a three-electrode system.

Example 1

With (Ni)_0.4Co_0.4P_0.2)₉₇Ru₃Amorphous nanocrystalline alloy ribbon as precursorPreparing a target electrode by the following steps:

step one, preparing target components;

according to (Ni)_0.4Co_0.4P_0.2)₉₇Ru₃The target components of (1) Ni, Co, P and Ru simple substance elements are weighed in sequence, and the purity of each element is not lower than 99.9%;

step two, preparing a master alloy;

step 21, smelting Ni and P by using a vacuum induction smelting furnace, wherein the smelting protective atmosphere is argon with the mass percent of 99.999 percent, and the vacuum degree is 3 multiplied by 10^-3Pa, smelting current of 80A for 6min to prepare a NiP pre-alloyed ingot;

22, putting the NiP pre-alloyed ingot and the elements of Co and Ru into a vacuum arc melting furnace for melting, wherein the melting protective atmosphere is argon with the mass percent of 99.999 percent, and the vacuum degree is 7.6 multiplied by 10^-3Pa, smelting current of 90A, smelting for 2min, and smelting for 8 times to prepare (Ni)_0.4Co_0.4P_0.2)₉₇Ru₃A master alloy ingot;

thirdly, preparing an amorphous nanocrystalline alloy thin strip by a melt spinning method;

the (Ni) obtained in the second step_0.4Co_0.4P_0.2)₉₇Ru₃The mother alloy is mechanically crushed into small pieces and is preset in a quartz tube, the outlet width at the bottom of the quartz tube is 4mm, and the small pieces are put into a vacuum induction melting furnace of a rapid solidification device along with the quartz tube to ensure that the diameter is 0.94 multiplied by 10^-2Introducing 99.0 wt% argon gas of 0.05MPa below Pa, heating to melt completely, spraying onto copper wheel rotating at high speed at spraying pressure of 0.02MPa and rotation speed of 23m/s to obtain (Ni)_0.4Co_0.4P_0.2)₉₇Ru₃An amorphous nanocrystalline alloy ribbon;

and (4) carrying out structural analysis on the sample prepared in the third step by using a Bruker AXS D8 type X-ray diffractometer, and adopting Ka rays of a copper target or a cobalt target. In the detection process, the scanning speed is 2 degrees/min, the scanning angle range is 20 degrees-80 degrees, the working voltage is 40kV, and the working current is 40 mA. The X-ray diffraction pattern is shown in figure 1, the abscissa is diffraction angle, the ordinate is relative intensity, the surface of the sample prepared by the step three is an amorphous nanocrystalline structure, and the core of the sample is an amorphous structure.

Selectively corroding to prepare a nano porous structure;

step 41, using conductive adhesive to connect the copper wire and the (Ni) obtained in step three_0.4Co_0.4P_0.2)₉₇Ru₃The non-test end of the amorphous nanocrystalline alloy thin strip is fixedly connected, and the non-test end is sealed with a non-conductive resin to expose (Ni)_0.4Co_0.4P_0.2)₉₇R_u3The free surface of the amorphous nanocrystalline alloy ribbon;

step 42, adding (Ni)_0.4Co_0.4P_0.2)₉₇Ru₃The free surface of the amorphous nanocrystalline alloy thin strip is used as a working electrode, a graphite rod with the diameter of 3mm and the length of 100mm is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode;

43, adopting a three-electrode method, and selecting 0.5M H₂SO₄Performing constant potential corrosion on the solution at a corrosion potential of 0.3V (vs. SCE) for 15min at a corrosion temperature of 298K to obtain (Ni) with a nano-porous structure on the surface_0.4Co_0.4P_0.2)₉₇Ru₃Amorphous alloy thin strip.

Step five, cleaning treatment;

the (Ni) with the surface having the nano-porous structure prepared in the fourth step_0.4Co_0.4P_0.2)₉₇Ru₃Washing the amorphous alloy thin strip for 3 times by using deionized water, and then washing for 3 times by using absolute ethyl alcohol; placing into a vacuum drying oven, treating at 60 deg.C for 30min, cooling to room temperature, and taking out to obtain (Ni) with nano porous structure on surface_0.4Co_0.4P_0.2)₉₇Ru₃An oxygen evolution catalytic material.

Structural and performance characterization

And (4) carrying out structural analysis on the sample prepared in the fifth step by using an X-ray diffractometer, wherein the surface of the sample prepared in the fifth step is of an amorphous structure as shown in figure 2.

The sample obtained in example 1 was observed by using a JSM-7500F field emission scanning electron microscope, and as shown in FIG. 3, the upper surface was shown to have a porous structure.

The samples obtained in example 1 were analyzed by means of a photoelectron spectrometer of the VG Scientific ESCALab220i-XL type, as shown in FIGS. 4, 5, 6, 7 and 8. The excitation source is Al K alpha X-ray with power about 300W. The base vacuum during analysis was 3X 10^-9mbar. The electron binding energy was corrected for the C1s peak (284.8eV) of the contaminated carbon. Statellite peak satellite peak. Fig. 4, 5, 6, 7 and 8 are high resolution spectra of Ru3d, Co2P, Ni2P, O1s and P2P, respectively.

When the cross section of the sample prepared in example 1 was observed with a JEOL JEM2010F transmission electron microscope, as shown in FIG. 9, it was revealed that the sample had a two-layer structure (as shown in FIG. 9A) in which one layer was surface-doped with NiO and Ni (OH) having high catalytic activity₂、CoO、Co(OH)₂、Ru、RuO₂、(PO₄)^3－One layer of highly conductive (Ni)_0.4Co_0.4P_0.2)₉₇Ru₃Amorphous alloy matrix, as shown in fig. 9B.

The sample prepared in the example 1 was subjected to an electrochemical experiment at 298K using a Princeton Applied Research VersaSTAT 3 electrochemical workstation, a conventional three-electrode system was used, a graphite rod 3mm in diameter and 100mm in length was used as an auxiliary electrode, a saturated calomel electrode was used as a reference electrode, a copper wire was fixedly connected to the non-test end of the corroded alloy ribbon with a conductive adhesive, the non-test end was sealed with a non-conductive resin, the free surface of the alloy ribbon was exposed, and the working electrode was used for an oxygen evolution performance test, the electrolyte was a 1mol/L KOH solution, and the scanning speed of the zeta potential polarization curve was 2 mV/s.

The test result shows that: the oxygen evolution catalysis curve of the Ru-doped NiCo-based composite prepared in example 1 is shown in FIG. 10 at 10mA/cm²The oxygen evolution geometric overpotential under current density is 240mV, the oxygen evolution catalytic reaction Tafel curve is shown in FIG. 11, the slope is 32mV/dec, as shown in FIG. 12 at 10And 100mA/cm²The prepared NiCo-based composite material doped with Ru has excellent anode oxygen evolution catalytic performance.

The ingredients in the following table were prepared using the preparation method of example 1:

example 2

With (Ni)_0.4Fe_0.4B_0.2)₉₇Ru₃The preparation method of the target electrode by taking the amorphous nanocrystalline alloy thin strip as a precursor comprises the following steps:

step one, preparing target components;

according to (Ni)_0.4Fe_0.4B_0.2)₉₇Ru₃Sequentially weighing Ni, Fe, B and Ru simple substance elements in a target component, wherein the purity of each element is not lower than 99.0%;

secondly, preparing master alloy;

putting weighed Ni, Fe, B and Ru into a vacuum arc melting furnace for melting, wherein the melting protective atmosphere is argon with the mass percent of 99.999 percent, and the vacuum degree is 8 multiplied by 10^-3Pa, smelting current of 90A, smelting for 2min, and smelting for 5 times to prepare (Ni)_0.4Fe_0.4B_0.2)₉₇Ru₃A master alloy ingot;

thirdly, preparing an amorphous nanocrystalline alloy thin strip by a melt spinning method;

the (Ni) obtained in the second step_0.4Fe_0.4B_0.2)₉₇Ru₃The mother alloy is mechanically crushed into small pieces and is preset in a quartz tube, the outlet width at the bottom of the quartz tube is 4mm, and the small pieces are put into a vacuum induction melting furnace of a rapid solidification device along with the quartz tube to ensure that the diameter is 0.9 multiplied by 10^-1Under Pa, charging argon gas of 0.05MPa and 99.0 wt%, inducing current of the coil to 6.7A, heating to melt completely, and sprayingSpraying pressure on a copper wheel rotating at a high speed of 0.02MPa, and the rotational linear speed of the copper wheel is 23m/s to obtain (Ni)_0.4Fe_0.4B_0.2)₉₇Ru₃An amorphous nanocrystalline alloy ribbon;

and (4) carrying out structural analysis on the sample prepared in the third step by using a Bruker AXS D8 type X-ray diffractometer, and adopting Ka rays of a copper target or a cobalt target. In the detection process, the scanning speed is 2 degrees/min, the scanning angle range is 20 degrees-80 degrees, the working voltage is 40kV, and the working current is 40 mA.

Selectively corroding to prepare a nano porous structure;

step 41, using conductive adhesive to connect the copper wire and the (Ni) obtained in step three_0.4Fe_0.4B_0.2)₉₇Ru₃The non-test end of the amorphous nanocrystalline alloy thin strip is fixedly connected, and the non-test portion is sealed with a non-conductive resin to expose (Ni)_0.4Fe_0.4B_0.2)₉₇Ru₃The free surface of the amorphous nanocrystalline alloy ribbon;

step 42, adding (Ni)_0.4Fe_0.4B_0.2)₉₇Ru₃The free surface of the amorphous nanocrystalline alloy thin strip is used as a working electrode, a graphite rod with the diameter of 3mm and the length of 100mm is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode;

43, adopting a three-electrode method, and selecting 0.3M H₂SO₄Performing constant potential corrosion on the solution at a corrosion potential of 0V (vs. SCE) for 25min at a corrosion temperature of 298K to obtain (Ni) with a nano-porous structure on the surface_0.4Fe_0.4B_0.2)₉₇Ru₃Amorphous alloy thin strip

Step five, cleaning treatment;

the (Ni) with the surface having the nano-porous structure prepared in the fourth step_0.4Fe_0.4B_0.2)₉₇Ru₃Washing the amorphous alloy thin strip for 3 times by using deionized water, and then washing for 3 times by using absolute ethyl alcohol; placing into a vacuum drying oven, treating at 60 deg.C for 30min, cooling to room temperature, and taking out to obtain the final product with nano-porous structure on surface(Ni_0.4Fe_0.4B_0.2)₉₇Ru₃Oxygen evolution catalytic material

Structural and performance characterization

The sample obtained in example 2 was subjected to structural analysis using an X-ray diffractometer.

The sample prepared in example 2 was observed using a JSM-7500F field emission scanning electron microscope.

The sample obtained in example 2 was analyzed by means of a photoelectron spectrometer of the type VG Scientific ESCALab220 i-XL. The excitation source is Al K alpha X-ray with power about 300W. The base vacuum during analysis was 3X 10^-9mbar. The electron binding energy was corrected for the C1s peak (284.8eV) of the contaminated carbon.

The cross section of the sample prepared in example 2 was observed with a JEOL JEM2010F transmission electron microscope.

The sample prepared in the example 2 was subjected to an electrochemical experiment at 298K using a Princeton Applied Research VersaSTAT 3 electrochemical workstation, a conventional three-electrode system was used, a graphite rod 3mm in diameter and 100mm in length was used as an auxiliary electrode, a saturated calomel electrode was used as a reference electrode, a copper wire was fixedly connected to the non-test end of the corroded alloy ribbon with a conductive adhesive, the non-test end was sealed with a non-conductive resin, the free surface of the alloy ribbon was exposed, and the working electrode was used for an oxygen evolution performance test, the electrolyte was a 1mol/L KOH solution, and the scanning speed of the zeta potential polarization curve was 2 mV/s.

The test result shows that: the Ru-doped NiFe-based composite prepared in example 2 was at 10mA/cm²The oxygen evolution geometric overpotential under the current density is 248mV, the oxygen evolution reaction tower Phil slope is 32mV/dec, and the oxygen evolution reaction tower Phil slope is 10mA/cm and 100mA/cm²The prepared NiFe-based material doped with Ru has excellent anodic oxygen evolution catalytic performance.

Example 3

With (Ni)_0.4Fe_0.4B_0.2)₉₇Ru_1.5Ir_1.5Preparation of amorphous nanocrystalline alloy ribbon as precursorThe target electrode is prepared by the following steps:

step one, preparing target components;

according to (Ni)_0.4Fe_0.4B_0.2)₉₇Ru_1.5Ir_1.5The target components of (1) Ni, Fe, B, Ru and Ir simple substance elements are weighed in sequence, and the purity of each element is not lower than 99.0%;

secondly, preparing master alloy;

putting weighed Ni, Fe, B, Ru and Ir into a vacuum arc melting furnace for melting, wherein the melting protective atmosphere is argon with the mass percentage of 99.999%; the vacuum degree is 7.8 multiplied by 10^-3Pa, smelting current of 90A, smelting for 2min, and smelting for 6 times to prepare (Ni)_0.4Fe_0.4B_0.2)₉₇Ru_1.5Ir_1.5A master alloy ingot.

Thirdly, preparing an amorphous nanocrystalline alloy thin strip by a melt spinning method;

mechanically crushing the mother alloy prepared in the step two into small pieces, then presetting the small pieces in a quartz tube, wherein the outlet width at the bottom of the quartz tube is 4mm, putting the small pieces together with the quartz tube into a vacuum induction smelting furnace of a rapid solidification device, and ensuring that the width is 0.8 multiplied by 10^-1Introducing 99.0 wt% argon gas under Pa of 0.05MPa, heating to melt completely, spraying onto copper wheel rotating at high speed under 0.02MPa and rotation speed of 22m/s to obtain (Ni)_0.4Fe_0.4B_0.2)₉₇Ru_1.5Ir_1.5An amorphous nanocrystalline alloy ribbon;

and (4) carrying out structural analysis on the sample prepared in the third step by using a Bruker AXS D8 type X-ray diffractometer, and adopting Ka rays of a copper target or a cobalt target. In the detection process, the scanning speed is 2 degrees/min, the scanning angle range is 20 degrees-80 degrees, the working voltage is 40kV, and the working current is 40 mA.

Selectively corroding to prepare a nano porous structure;

step 41, using conductive adhesive to connect the copper wire and the (Ni) obtained in step three_0.4Fe_0.4B_0.2)₉₇Ru_1.5Ir_1.5The non-test end of the amorphous nanocrystalline alloy thin strip is fixedly connected, and the non-test portion is sealed with a non-conductive resin to expose (Ni)_0.4Fe_0.4B_0.2)₉₇Ru_1.5Ir_1.5The free surface of the amorphous nanocrystalline alloy ribbon;

step 42, adding (Ni)_0.4Fe_0.4B_0.2)₉₇Ru_1.5Ir_1.5The free surface of the amorphous nanocrystalline alloy thin strip is used as a working electrode, a graphite rod with the diameter of 3mm and the length of 100mm is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode;

43, adopting a three-electrode method, and selecting 0.3M H₂SO₄Performing constant potential corrosion on the solution at a corrosion potential of 0V (vs. SCE) for 25min at a corrosion temperature of 298K to obtain (Ni) with a nano-porous structure on the surface_0.4Fe_0.4B_0.2)₉₇Ru_1.5Ir_1.5Amorphous alloy thin strip.

Step five, cleaning treatment;

the (Ni) with the surface having the nano-porous structure prepared in the fourth step_0.4Fe_0.4B_0.2)₉₇Ru_1.5Ir_1.5Washing the amorphous alloy thin strip for 3 times by using deionized water, and then washing for 3 times by using absolute ethyl alcohol; placing into a vacuum drying oven, treating at 60 deg.C for 30min, cooling to room temperature, and taking out to obtain (Ni) with nano porous structure on surface_0.4Fe_0.4B_0.2)₉₇Ru_1.5Ir_1.5An oxygen evolution catalytic material.

Structural and performance characterization

The sample obtained in example 3 was subjected to structural analysis using an X-ray diffractometer.

The sample prepared in example 3 was observed using a JSM-7500F field emission scanning electron microscope.

The sample obtained in example 3 was analyzed by means of a photoelectron spectrometer model VG Scientific ESCALab220 i-XL. The excitation source is Al K alpha X-ray with power about 300W. The base vacuum during analysis was 3X 10^-9mbar. Contamination by electron binding energyThe peak C1s for carbon (284.8eV) was corrected.

The cross section of the sample prepared in example 3 was observed with a JEOL JEM2010F transmission electron microscope.

The sample prepared in the example 3 was subjected to an electrochemical experiment at 298K using a Princeton Applied Research VersaSTAT 3 electrochemical workstation, a conventional three-electrode system was used, a graphite rod having a diameter of 3mm and a length of 100mm was used as an auxiliary electrode, a saturated calomel electrode was used as a reference electrode, a copper wire was fixedly connected to the non-test end of the corroded alloy ribbon using a conductive adhesive, the non-test end was sealed with a non-conductive resin, the free surface of the alloy ribbon was exposed, and the working electrode was used for an oxygen evolution performance test, the electrolyte was a 1mol/L KOH solution, and the scanning speed of the zeta potential polarization curve was 2 mV/s.

The test result shows that: the NiFe-based composite material doped with Ru and Ir prepared in example 3 is at 10mA/cm²The oxygen evolution geometric overpotential under current density is 210mV, the oxygen evolution reaction tower Phil slope is 30mV/dec, at 10 and 100mA/cm²The prepared NiFe-based composite material doped with Ru and Ir has excellent anode oxygen evolution catalytic performance.

Example 4

With (Ni)_0.4Fe_0.4B_0.2)₉₇Ru_0.5Ir_0.5Rh_0.5Os_0.5Pt_0.5Pd_0.5The preparation method of the target electrode by taking the amorphous nanocrystalline alloy thin strip as a precursor comprises the following steps:

step one, preparing target components;

according to (Ni)_0.4Fe_0.4B_0.2)₉₇Ru_0.5Ir_0.5Rh_0.5Os_0.5Pt_0.5Pd_0.5The target components of the alloy are sequentially weighed to obtain Ni, Fe, B, Ru, Ir, Rh, Os, Pt and Pd elementary substance elements, and the purity of each element is not lower than 99.0%;

secondly, preparing master alloy;

the target is the weighed Ni, Fe,B. Putting the Ru, Ir, Rh, Os, Pt and Pd into a vacuum arc melting furnace for melting, wherein the melting protective atmosphere is argon with the mass percent of 99.999%; the degree of vacuum was 6.2X 10^-3Pa, smelting current of 100A, smelting for 3min, and smelting for 10 times to prepare (Ni)_0.4Fe_0.4B_0.2)₉₇Ru_0.5Ir_0.5Rh_0.5Os_0.5Pt_0.5Pd_0.5A master alloy ingot;

thirdly, preparing an amorphous nanocrystalline alloy thin strip by a melt spinning method;

the (Ni) obtained in the second step_0.4Fe_0.4B_0.2)₉₇Ru_0.5Ir_0.5Rh_0.5Os_0.5Pt_0.5Pd_0.5The mother alloy is mechanically crushed into small pieces and is preset in a quartz tube, the outlet width at the bottom of the quartz tube is 4mm, and the small pieces are put into a vacuum induction melting furnace of a rapid solidification device along with the quartz tube to ensure that the width of the small pieces is 1 multiplied by 10^-2Introducing argon gas with a mass percent of 99.0% under Pa of 0.05MPa, heating to completely melt the alloy with an induction current of 8.3A, and spraying the alloy onto a copper wheel rotating at a high speed with a spraying pressure of 0.02MPa and a copper wheel rotating speed of 23m/s to obtain the (Ni) alloy_0.4Fe_0.4B_0.2)₉₇Ru_0.5Ir_0.5Rh_0.5Os_0.5Pt_0.5Pd_0.5An amorphous nanocrystalline alloy ribbon;

and (4) carrying out structural analysis on the sample prepared in the third step by using a Bruker AXS D8 type X-ray diffractometer, and adopting Ka rays of a copper target or a cobalt target. In the detection process, the scanning speed is 2 degrees/min, the scanning angle range is 20 degrees-80 degrees, the working voltage is 40kV, and the working current is 40 mA.

Selectively corroding to prepare a nano porous structure;

step 41, using conductive adhesive to connect the copper wire and the (Ni) prepared in step three_0.4Fe_0.4B_0.2)₉₇Ru_0.5Ir_0.5Rh_{0. 5}Os_0.5Pt_0.5Pd_0.5The non-test end of the amorphous nanocrystalline alloy thin strip is fixedly connected, and the non-test part is non-conductiveResin sealing to expose (Ni)_0.4Fe_0.4B_0.2)₉₇Ru_0.5Ir_0.5Rh_0.5Os_0.5Pt_0.5Pd_0.5The free surface of the amorphous nanocrystalline alloy ribbon;

step 42, adding (Ni)_0.4Fe_0.4B_0.2)₉₇Ru_0.5Ir_0.5Rh_0.5Os_0.5Pt_0.5Pd_0.5The free surface of the amorphous nanocrystalline alloy thin strip is used as a working electrode, a graphite rod with the diameter of 3mm and the length of 100mm is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode;

43, adopting a three-electrode method, and selecting 0.3M H₂SO₄Performing constant potential corrosion on the solution at a corrosion potential of 0V (vs. SCE) for 15min at a corrosion temperature of 298K to obtain (Ni) with a nano-porous structure on the surface_0.4Fe_0.4B_0.2)₉₇Ru_0.5Ir_0.5Rh_0.5Os_0.5Pt_0.5Pd_0.5Amorphous alloy thin strip.

Step five, cleaning treatment;

the (Ni) with the surface having the nano-porous structure prepared in the fourth step_0.4Fe_0.4B_0.2)₉₇Ru_0.5Ir_0.5Rh_0.5Os_0.5Pt_0.5Pd_0.5Washing the amorphous alloy thin strip for 3 times by using deionized water, and then washing for 3 times by using absolute ethyl alcohol; placing into a vacuum drying oven, treating at 60 deg.C for 30min, cooling to room temperature, and taking out to obtain (Ni) with nano porous structure on surface_0.4Fe_0.4B_0.2)₉₇Ru_0.5Ir_0.5Rh_0.5Os_0.5Pt_0.5Pd_0.5An oxygen evolution catalytic material.

Structural and performance characterization

The sample obtained in example 4 was subjected to structural analysis using an X-ray diffractometer.

The sample prepared in example 4 was observed using a JSM-7500F field emission scanning electron microscope.

The sample obtained in example 4 was analyzed by means of a photoelectron spectrometer model VG Scientific ESCALab220 i-XL. The excitation source is Al K alpha X-ray with power about 300W. The base vacuum during analysis was 3X 10^-9mbar. The electron binding energy was corrected for the C1s peak (284.8eV) of the contaminated carbon.

The cross section of the sample prepared in example 4 was observed with a JEOL JEM2010F transmission electron microscope

The sample prepared in the example 4 was subjected to an electrochemical experiment at 298K using a Princeton Applied Research VersaSTAT 3 electrochemical workstation, a conventional three-electrode system was used, a graphite rod having a diameter of 3mm and a length of 100mm was used as an auxiliary electrode, a saturated calomel electrode was used as a reference electrode, a copper wire was fixedly connected to the non-test end of the corroded alloy ribbon using a conductive adhesive, the non-test end was sealed with a non-conductive resin, the free surface of the alloy ribbon was exposed, and the working electrode was used for an oxygen evolution performance test, the electrolyte was a 1mol/L KOH solution, and the scanning speed of the zeta potential polarization curve was 2 mV/s.

The test result shows that the NiFe-based composite material doped with Ru, Ir, Rh, Os, Pt and Pd prepared in the example 4 is at 10mA/cm²The oxygen evolution geometric overpotential under current density is 186mV, the oxygen evolution reaction tower Phil slope is 32mV/dec, at 10 and 100mA/cm²The prepared NiFe-based composite material doped with Ru, Ir, Rh, Os, Pt and Pd has excellent anodic oxygen evolution catalytic performance.

Example 5

With (Fe)_0.6Co_0.2P_0.2)₉₄Rh₁Os₁Ag₁Au₁Pt₁Pd₁The preparation method of the target electrode by taking the amorphous nanocrystalline alloy thin strip as a precursor comprises the following steps:

step one, preparing target components;

according to the object (Fe)_0.6Co_0.2P_0.2)₉₄Rh₁Os₁Ag₁Au₁Pt₁Pd₁The target component of (1) sequentially weighing Fe, Co, P, Rh, Os, Ag, Au, Pt and Pd elementary elements, wherein the purity of each element is not lower than 99.0%;

step two, preparing a master alloy;

step 21, smelting Fe and P in a vacuum induction smelting furnace in a smelting protective atmosphere of 99.999 percent by mass of argon and a vacuum degree of 3 multiplied by 10^-3Pa, smelting current of 80A for 6min to prepare a FeP pre-alloy ingot;

step 22, putting the FeP pre-alloy ingot and elements of Co, Rh, Os, Ag, Au, Pt and Pd into a vacuum arc melting furnace for melting, wherein the melting protective atmosphere is argon with the mass percentage of 99.999%; the vacuum degree is 6.5X 10^-3Pa, smelting current of 95A for 3min, and smelting for 10 times to prepare (Fe)_0.6Co_0.2P_0.2)₉₄Rh₁Os₁Ag₁Au₁Pt₁Pd₁A master alloy ingot;

thirdly, preparing an amorphous nanocrystalline alloy thin strip by a melt spinning method;

the (Fe) prepared in the second step_0.6Co_0.2P_0.2)₉₄Rh₁Os₁Ag₁Au₁Pt₁Pd₁The mother alloy is mechanically crushed into small pieces and is preset in a quartz tube, the outlet width at the bottom of the quartz tube is 4mm, and the small pieces are put into a vacuum induction melting furnace of a rapid solidification device along with the quartz tube to ensure that the diameter of the small pieces is 1.2 multiplied by 10^-2Under Pa, charging 0.05MPa of argon gas with a mass percent of 99.0%, heating to melt completely, spraying onto a copper wheel rotating at a high speed with a spraying pressure of 0.02MPa and a rotation speed of 23m/s to obtain (Fe)_0.6Co_0.2P_0.2)₉₄Rh₁Os₁Ag₁Au₁Pt₁Pd₁An amorphous nanocrystalline alloy ribbon;

and (4) carrying out structural analysis on the sample prepared in the third step by using a Bruker AXS D8 type X-ray diffractometer, and adopting Ka rays of a copper target or a cobalt target. In the detection process, the scanning speed is 2 degrees/min, the scanning angle range is 20 degrees-80 degrees, the working voltage is 40kV, and the working current is 40 mA;

selectively corroding to prepare a nano porous structure;

step 41, using conductive adhesive to connect the copper wire and the (Fe) prepared in step three_0.6Co_0.2P_0.2)₉₄Rh₁Os₁Ag₁Au₁Pt₁Pd₁Fixedly connecting the amorphous nanocrystalline alloy thin strips, sealing the non-test part with non-conductive resin, and exposing (Fe)_0.6Co_0.2P_0.2)₉₄Rh₁Os₁Ag₁Au₁Pt₁Pd₁The free surface of the amorphous nanocrystalline alloy ribbon;

step 42, mixing (Fe)_0.6Co_0.2P_0.2)₉₄Rh₁Os₁Ag₁Au₁Pt₁Pd₁The free surface of the amorphous nanocrystalline alloy thin strip is used as a working electrode, a graphite rod with the diameter of 3mm and the length of 100mm is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode;

43, adopting a three-electrode method, and selecting 0.3M H₃PO₄Performing constant potential corrosion on the solution at a corrosion potential of 0V (vs. SCE) for 25min at a corrosion temperature of 298K to obtain (Fe) with a nano-porous structure on the surface_0.6Co_0.2P_0.2)₉₄Rh₁Os₁Ag₁Au₁Pt₁Pd₁Amorphous alloy thin strip.

Step five, cleaning treatment;

the (Fe) with the surface having the nano-porous structure prepared in the fourth step_0.6Co_0.2P_0.2)₉₄Rh₁Os₁Ag₁Au₁Pt₁Pd₁Washing the amorphous alloy thin strip for 3 times by using deionized water, and then washing for 3 times by using absolute ethyl alcohol; placing into a vacuum drying oven, treating at 60 deg.C for 30min, cooling to room temperature, and taking out to obtain the final product (Fe) with nano-porous structure on surface_0.6Co_0.2P_0.2)₉₄Rh₁Os₁Ag₁Au₁Pt₁Pd₁An oxygen evolution catalytic material.

Structural and performance characterization

The sample obtained in example 5 was subjected to structural analysis using an X-ray diffractometer.

The sample prepared in example 5 was observed using a JSM-7500F field emission scanning electron microscope.

The sample obtained in example 5 was analyzed by means of a photoelectron spectrometer model VG Scientific ESCALab220 i-XL. The excitation source is Al K alpha X-ray with power about 300W. The base vacuum during analysis was 3X 10^-9mbar. The electron binding energy was corrected for the C1s peak (284.8eV) of the contaminated carbon.

The cross section of the sample prepared in example 5 was observed with a JEOL JEM2010F transmission electron microscope

The sample prepared in example 5 was subjected to an electrochemical experiment at 298K using a Princeton Applied Research VersaSTAT 3 electrochemical workstation, a conventional three-electrode system was used, a graphite rod having a diameter of 3mm and a length of 100mm was used as an auxiliary electrode, a saturated calomel electrode was used as a reference electrode, a copper wire was fixedly connected to the non-test end of the corroded alloy ribbon using a conductive adhesive, the non-test end was sealed with a non-conductive resin, the free surface of the alloy ribbon was exposed, and the working electrode was used for an oxygen evolution performance test, the electrolyte was a 1mol/L KOH solution, and the scanning speed of the zeta potential polarization curve was 2 mV/s.

The test results showed that the Rh, Os, Ag, Au, Pt and Pd doped FeCo-based composite material prepared in example 5 was at 10mA/cm²The oxygen evolution geometric overpotential under the current density is 268mV, the oxygen evolution reaction tower Phil slope is 63mV/dec, at 10 and 100mA/cm²The prepared FeCo-based composite material doped with Rh, Os, Ag, Au, Pt and Pd has excellent anode oxygen evolution catalytic performance.

Example 6

With (Fe)_0.4Co_0.4B_0.1P_0.1)₉₇Ru_1.5Ir_1.5The preparation method of the target electrode by taking the amorphous nanocrystalline alloy thin strip as a precursor comprises the following steps:

step one, preparing target components;

according to (Fe)_0.4Co_0.4B_0.1P_0.1)₉₇Ru_1.5Ir_1.5The target components of (1) sequentially and targetedly weighing simple substance elements of Fe, Co, B, P, Ru and Ir, and the purity of each element is not lower than 99.0%;

step two, preparing a master alloy;

step 21, smelting Fe and P in a vacuum induction smelting furnace in a smelting protective atmosphere of 99.999 percent by mass of argon and a vacuum degree of 3 multiplied by 10^-3Pa, smelting for 6min at a smelting current of 80A to prepare a FeP pre-alloy ingot, and then putting the FeP pre-alloy ingot and the rest elements into a vacuum arc smelting furnace to be smelted uniformly to obtain a master alloy ingot;

step 22, putting the FeP pre-alloy ingot and the elements of Co, B, Ru and Ir into a vacuum arc melting furnace for melting, wherein the melting protective atmosphere is argon with the mass percentage of 99.999 percent; the degree of vacuum was 7.0X 10^-3Pa, the smelting current is 90A, the smelting is carried out for 2min, and the smelting is carried out for 8 times to prepare (Fe)_0.4Co_0.4B_0.1P_0.1)₉₇Ru_1.5Ir_1.5Amorphous nanocrystalline alloy ribbon.

Thirdly, preparing an amorphous nanocrystalline alloy thin strip by a melt spinning method;

the (Fe) prepared in the second step_0.4Co_0.4B_0.1P_0.1)₉₇Ru_1.5Ir_1.5The mother alloy is mechanically crushed into small pieces and is preset in a quartz tube, the outlet width at the bottom of the quartz tube is 4mm, and the small pieces are put into a vacuum induction melting furnace of a rapid solidification device along with the quartz tube to ensure that the width of the small pieces is 1 multiplied by 10^-2Under Pa, charging 0.05MPa of argon gas with a mass percent of 99.0%, heating to melt completely, spraying onto a copper wheel rotating at a high speed with a spraying pressure of 0.02MPa and a rotation speed of 23m/s to obtain (Fe)_0.4Co_0.4B_0.1P_0.1)₉₇Ru_1.5Ir_1.5An amorphous nanocrystalline alloy ribbon;

and (4) carrying out structural analysis on the sample prepared in the third step by using a Bruker AXS D8 type X-ray diffractometer, and adopting Ka rays of a copper target or a cobalt target. In the detection process, the scanning speed is 2 degrees/min, the scanning angle range is 20 degrees-80 degrees, the working voltage is 40kV, and the working current is 40 mA;

selectively corroding to prepare a nano porous structure;

step 41, using conductive adhesive to connect the copper wire and the (Fe) prepared in step three_0.4Co_0.4B_0.1P_0.1)₉₇Ru_1.5Ir_1.5Fixedly connecting the amorphous nanocrystalline alloy thin strips, sealing the non-test part with non-conductive resin, and exposing (Fe)_0.4Co_0.4B_0.1P_0.1)₉₇Ru_1.5Ir_1.5The free surface of the amorphous nanocrystalline alloy ribbon;

step 42, mixing (Fe)_0.4Co_0.4B_0.1P_0.1)₉₇Ru_1.5Ir_1.5The free surface of the amorphous nanocrystalline alloy thin strip is used as a working electrode, a graphite rod with the diameter of 3mm and the length of 100mm is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode;

43, adopting a three-electrode method, and selecting 0.3M H₃PO₄Performing constant potential corrosion on the solution at a corrosion potential of 0V (vs. SCE) for 30min at a corrosion temperature of 298K to obtain (Fe) with a nano-porous structure on the surface_0.4Co_0.4B_0.1P_0.1)₉₇Ru_1.5Ir_1.5Amorphous alloy thin strip.

Step five, cleaning treatment;

the (Fe) with the surface having the nano-porous structure prepared in the fourth step_0.4Co_0.4B_0.1P_0.1)₉₇Ru_1.5Ir_1.5Washing the amorphous alloy thin strip for 3 times by using deionized water, and then washing for 3 times by using absolute ethyl alcohol; placing into a vacuum drying oven, treating at 60 deg.C for 30min, cooling to room temperature, and taking out to obtain the final product (Fe) with nano-porous structure on surface_0.4Co_0.4B_0.1P_0.1)₉₇Ru_1.5Ir_1.5An oxygen evolution catalytic material.

Structural and performance characterization

The sample obtained in example 6 was subjected to structural analysis using an X-ray diffractometer.

The sample prepared in example 6 was observed with a JSM-7500F field emission scanning electron microscope.

The sample obtained in example 6 was analyzed by means of a photoelectron spectrometer model VG Scientific ESCALab220 i-XL. The excitation source is Al K alpha X-ray with power about 300W. The base vacuum during analysis was 3X 10^-9mbar. The electron binding energy was corrected for the C1s peak (284.8eV) of the contaminated carbon.

The cross section of the sample prepared in example 6 was observed with a JEOL JEM2010F transmission electron microscope

The sample prepared in example 6 was subjected to an electrochemical experiment at 298K using a Princeton Applied Research VersaSTAT 3 electrochemical workstation, a conventional three-electrode system was used, a graphite rod 3mm in diameter and 100mm in length was used as an auxiliary electrode, a saturated calomel electrode was used as a reference electrode, a copper wire was fixedly connected to the non-test end of the corroded alloy ribbon with a conductive adhesive, the non-test end was sealed with a non-conductive resin, the free surface of the alloy ribbon was exposed, and the working electrode was used for an oxygen evolution performance test, the electrolyte was a 1mol/L KOH solution, and the scanning speed of the zeta potential polarization curve was 2 mV/s.

The test result shows that the FeCo-based composite material doped with Ru and Ir prepared in the example 6 is at 10mA/cm²The oxygen evolution geometric overpotential under current density is 250mV, the oxygen evolution reaction tower Phil slope is 63mV/dec, at 10 and 100mA/cm²The prepared FeCo-based composite material doped with Ru and Ir has excellent anode oxygen evolution catalytic performance.

Example 7

With (Ni)_0.4Co_0.4P_0.10C_0.05Si_0.05)₉₀Ru₅Ir₃Pt₁Pd₁The preparation method of the target electrode by taking the amorphous nanocrystalline alloy thin strip as a precursor comprises the following steps:

step one, preparing target components;

according to (Ni)_0.4Co_0.4P_0.10C_0.05Si_0.05)₉₀Ru₅Ir₃Pt₁Pd₁The target components of (1) Ni, Co, P, C, Si, Ru, Ir, Pt and Pd are sequentially weighed according to the target, and the purity of each element is not lower than 99.0%;

step two, preparing a master alloy;

step 21, smelting Ni and P by using a vacuum induction smelting furnace, wherein the smelting protective atmosphere is argon with the mass percent of 99.999 percent, and the vacuum degree is 3 multiplied by 10^-3Pa, smelting current of 80A for 6min to prepare a NiP pre-alloyed ingot;

step 22, putting the NiP pre-alloyed ingot and elements of Co, C, Si, Ru, Ir, Pt and Pd into a vacuum arc melting furnace for melting, wherein the melting protective atmosphere is argon with the mass percentage of 99.999%; the vacuum degree is 6.7X 10^-3Pa, smelting current of 95A, smelting for 3min, and smelting for 10 times to prepare (Ni)_0.4Co_0.4P_0.10C_0.05Si_0.05)₉₀Ru₅Ir₃Pt₁Pd₁A master alloy ingot.

Thirdly, preparing an amorphous nanocrystalline alloy thin strip by a melt spinning method;

the (Ni) obtained in the second step_0.4Co_0.4P_0.10C_0.05Si_0.05)₉₀Ru₅Ir₃Pt₁Pd₁The mother alloy is mechanically crushed into small pieces and is preset in a quartz tube, the outlet width at the bottom of the quartz tube is 4mm, and the small pieces are put into a vacuum induction melting furnace of a rapid solidification device along with the quartz tube to ensure that the diameter is 7 multiplied by 10^-2Introducing argon gas with a mass percent of 99.0% under Pa of 0.05MPa, heating to completely melt the argon gas with a coil induction current of 7.3A, and spraying the molten argon gas onto a copper wheel rotating at a high speed with a spraying pressure of 0.02MPa and a copper wheel rotating speed of 23m/s to obtain the (Ni) alloy_0.4Co_0.4P_0.10C_0.05Si_0.05)₉₀Ru₅Ir₃Pt₁Pd₁An amorphous nanocrystalline alloy ribbon;

and (4) carrying out structural analysis on the sample prepared in the third step by using a Bruker AXS D8 type X-ray diffractometer, and adopting Ka rays of a copper target or a cobalt target. In the detection process, the scanning speed is 2 degrees/min, the scanning angle range is 20 degrees-80 degrees, the working voltage is 40kV, and the working current is 40 mA;

selectively corroding to prepare a nano porous structure;

step 41, using conductive adhesive to connect the copper wire and the (Ni) prepared in step three_0.4Co_0.4P_0.10C_0.05Si_0.05)₉₀Ru₅Ir₃Pt₁Pd₁Fixedly connecting the amorphous nanocrystalline alloy thin strip, sealing the non-test part with non-conductive resin to expose (Ni)_0.4Co_0.4P_0.10C_0.05Si_0.05)₉₀Ru₅Ir₃Pt₁Pd₁The free surface of the amorphous nanocrystalline alloy ribbon;

step 42, adding (Ni)_0.4Co_0.4P_0.10C_0.05Si_0.05)₉₀Ru₅Ir₃Pt₁Pd₁The free surface of the amorphous nanocrystalline alloy thin strip is used as a working electrode, a graphite rod with the diameter of 3mm and the length of 100mm is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode;

43, adopting a three-electrode method, and selecting 0.02M H₂SO₄Carrying out constant potential corrosion on the solution under the corrosion potential of 0V (vs. SCE), wherein the corrosion time is 30min, the corrosion temperature is 298K, and preparing the (Ni) with the surface having the nano-porous structure_0.4Co_0.4P_0.10C_0.05Si_0.05)₉₀Ru₅Ir₃Pt₁Pd₁An amorphous alloy thin strip;

step five, cleaning treatment;

the (Ni) with the surface having the nano-porous structure prepared in the fourth step_0.4Co_0.4P_0.10C_0.05Si_0.05)₉₀Ru₅Ir₃Pt₁Pd₁Washing the amorphous alloy thin strip for 3 times by using deionized water, and then washing for 3 times by using absolute ethyl alcohol; placing into a vacuum drying oven, treating at 60 deg.C for 30min, cooling to room temperature, and taking out to obtain (Ni) with nano porous structure on surface_0.4Co_0.4P_0.10C_0.05Si_0.05)₉₀Ru₅Ir₃Pt₁Pd₁An oxygen evolution catalytic material.

Structural and performance characterization

The sample obtained in example 7 was subjected to structural analysis using an X-ray diffractometer.

The sample prepared in example 7 was observed with a JSM-7500F field emission scanning electron microscope.

The sample obtained in example 7 was analyzed by means of a photoelectron spectrometer model VG Scientific ESCALab220 i-XL. The excitation source is Al K alpha X-ray with power about 300W. The base vacuum during analysis was 3X 10^-9mbar. The electron binding energy was corrected for the C1s peak (284.8eV) of the contaminated carbon. The cross section of the sample prepared in example 2 was observed with a JEOL JEM2010F transmission electron microscope

The cross section of the sample prepared in example 7 was observed with a JEOL JEM2010F transmission electron microscope

The sample prepared in example 7 was subjected to an electrochemical experiment at 298K using a Princeton Applied Research VersaSTAT 3 electrochemical workstation, a conventional three-electrode system was used, a graphite rod having a diameter of 3mm and a length of 100mm was used as an auxiliary electrode, a saturated calomel electrode was used as a reference electrode, a copper wire was fixedly connected to the non-test end of the corroded alloy ribbon using a conductive adhesive, the non-test end was sealed with a non-conductive resin, the free surface of the alloy ribbon was exposed, and the working electrode was used for an oxygen evolution performance test, the electrolyte was a 1mol/L KOH solution, and the scanning speed of the zeta potential polarization curve was 2 mV/s.

The test result shows that the NiCo-based composite material doped with Ru, Ir, Pt and Pd prepared in the example 7 is at 10mA/cm²At current densityThe oxygen evolution geometric overpotential is 220mV, the oxygen evolution reaction tower Phil slope is 63mV/dec, at 10 and 100mA/cm²The prepared NiCo-based composite material doped with Ru, Ir, Pt and Pd has excellent anode oxygen evolution catalytic performance.

Example 8

With the goal (Ni)_0.3Fe_0.3Co_0.2B_0.1P_0.1)₉₆Pt₁Pd₁Ag₁Au₁The preparation method of the target electrode by taking the amorphous nanocrystalline alloy thin strip as a precursor comprises the following steps:

step one, preparing target components;

according to (Ni)_0.3Fe_0.3Co_0.2B_0.1P_0.1)₉₆Pt₁Pd₁Ag₁Au₁The target components of the alloy are sequentially weighed to obtain simple substance elements of Ni, Fe, Co, B, P, Pt, Pd, Ag and Au, and the purity of each element is not lower than 99.0%;

step two, preparing a master alloy;

step 21, smelting Fe and P in a vacuum induction smelting furnace in a smelting protective atmosphere of 99.999 percent by mass of argon and a vacuum degree of 3 multiplied by 10^-3Pa, smelting current of 80A for 6min to prepare a FeP pre-alloy ingot;

step 22, putting the FeP pre-alloy ingot and the elements of Ni, Co, B, Pt, Pd, Ag and Au into a vacuum arc melting furnace for melting, wherein the melting protective atmosphere is argon with the mass percentage of 99.999%; the degree of vacuum was 5.3X 10^-3Pa, smelting current of 95A, smelting for 3min, and smelting for 10 times to prepare (Ni)_0.3Fe_0.3Co_0.2B_0.1P_0.1)₉₆Pt₁Pd₁Ag₁Au₁A master alloy ingot;

thirdly, preparing an amorphous nanocrystalline alloy thin strip by a melt spinning method;

the (Ni) obtained in the second step_0.3Fe_0.3Co_0.2B_0.1P_0.1)₉₆Pt₁Pd₁Ag₁Au₁The mother alloy is mechanically crushed into small pieces and is preset in a quartz tube, the outlet width at the bottom of the quartz tube is 4mm, and the small pieces are put into a vacuum induction melting furnace of a rapid solidification device along with the quartz tube to ensure that the diameter is 8.2 multiplied by 10^-2Introducing argon gas with a mass percent of 99.0% under Pa under 0.05MPa, inducing current of the coil to be 7.3A, heating to completely melt the alloy, and spraying the alloy onto a copper wheel rotating at a high speed, wherein the spraying pressure is 0.04MPa, and the rotation speed of the copper wheel is 21m/s to obtain the (Ni)_0.3Fe_0.3Co_0.2B_0.1P_0.1)₉₆Pt₁Pd₁Ag₁Au₁An amorphous nanocrystalline alloy ribbon;

and (4) carrying out structural analysis on the sample prepared in the third step by using a Bruker AXS D8 type X-ray diffractometer, and adopting Ka rays of a copper target or a cobalt target. In the detection process, the scanning speed is 2 degrees/min, the scanning angle range is 20 degrees-80 degrees, the working voltage is 40kV, and the working current is 40 mA;

selectively corroding to prepare a nano porous structure;

step 41, using conductive adhesive to connect the copper wire and the (Ni) prepared in step three_0.3Fe_0.3Co_0.2B_0.1P_0.1)₉₆Pt₁Pd₁Ag₁Au₁Fixedly connecting the amorphous nanocrystalline alloy thin strip, sealing the non-test part with non-conductive resin to expose (Ni)_0.3Fe_0.3Co_0.2B_0.1P_0.1)₉₆Pt₁Pd₁Ag₁Au₁A free surface of the amorphous nanocrystalline alloy ribbon;

step 42, adding (Ni)_0.3Fe_0.3Co_0.2B_0.1P_0.1)₉₆Pt₁Pd₁Ag₁Au₁The free surface of the amorphous nanocrystalline alloy thin strip is used as a working electrode, a graphite rod with the diameter of 3mm and the length of 100mm is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode;

43, adopting a three-electrode method, and selecting 0.3M H₃PO₄Solutions ofPerforming constant potential corrosion under the corrosion potential of 0.3V (vs. SCE), wherein the corrosion time is 25min, the corrosion temperature is 298K, and preparing the (Ni) with the surface having the nano-porous structure_0.3Fe_0.3Co_0.2B_0.1P_0.1)₉₆Pt₁Pd₁Ag₁Au₁Amorphous alloy thin strip.

Step five, cleaning treatment;

the (Ni) with the surface having the nano-porous structure prepared in the fourth step_0.3Fe_0.3Co_0.2B_0.1P_0.1)₉₆Pt₁Pd₁Ag₁Au₁Washing the amorphous alloy thin strip for 3 times by using deionized water, and then washing for 3 times by using absolute ethyl alcohol; placing into a vacuum drying oven, treating at 60 deg.C for 30min, cooling to room temperature, and taking out to obtain (Ni) with nano porous structure on surface_0.3Fe_0.3Co_0.2B_0.1P_0.1)₉₆Pt₁Pd₁Ag₁Au₁An oxygen evolution catalytic material.

Structural and performance characterization

The sample obtained in example 8 was subjected to structural analysis using an X-ray diffractometer.

The sample prepared in example 8 was observed using a JSM-7500F field emission scanning electron microscope.

The sample obtained in example 8 was analyzed by means of a photoelectron spectrometer model VG Scientific ESCALab220 i-XL. The excitation source is Al K alpha X-ray with power about 300W. The base vacuum during analysis was 3X 10^-9mbar. The electron binding energy was corrected for the C1s peak (284.8eV) of the contaminated carbon.

The cross section of the sample prepared in example 8 was observed with a JEOL JEM2010F transmission electron microscope

The sample prepared in the example 8 was subjected to an electrochemical experiment at 298K using a Princeton Applied Research VersaSTAT 3 electrochemical workstation, a conventional three-electrode system was used, a graphite rod having a diameter of 3mm and a length of 100mm was used as an auxiliary electrode, a saturated calomel electrode was used as a reference electrode, a copper wire was fixedly connected to the non-test end of the corroded alloy ribbon using a conductive adhesive, the non-test end was sealed with a non-conductive resin, the free surface of the alloy ribbon was exposed, and the working electrode was used for an oxygen evolution performance test, the electrolyte was a 1mol/L KOH solution, and the scanning speed of the zeta potential polarization curve was 2 mV/s.

The test result shows that the NiFeCo-based composite material doped with Pt, Pd, Ag and Au prepared in the example 8 is at 10mA/cm²The oxygen evolution geometric overpotential under the current density is 270mV, the oxygen evolution reaction tower Phil slope is 52mV/dec, at 10 and 100mA/cm²The prepared NiFeCo-based composite material doped with Pt, Pd, Ag and Au has excellent anodic oxygen evolution catalytic performance. Target

Example 9

With (Ni)_0.3Fe_0.3Co_0.2P_0.2)₉₆Ru_0.5Ir_0.5Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_0.5Au_0.5The preparation method of the target electrode by taking the amorphous nanocrystalline alloy thin strip as a precursor target comprises the following steps:

step one, preparing target components;

according to (Ni)_0.3Fe_0.3Co_0.2P_0.2)₉₆Ru_0.5Ir_0.5Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_0.5Au_0.5The target component of (1) sequentially weighing single elements of Ni, Fe, Co, P, Ru, Ir, Os, Rh, Pt, Pd, Ag and Au, wherein the purity of each element is not lower than 99.0%;

step two, preparing a master alloy;

step 21, smelting Fe and P in a vacuum induction smelting furnace in a smelting protective atmosphere of 99.999 percent by mass of argon and a vacuum degree of 3 multiplied by 10^-3Pa, smelting current of 80A for 6min to prepare a FeP pre-alloy ingot;

step 22, putting FeP pre-alloy ingot and Ni, Co, Ru, Ir, Os, Rh, Pt, Pd, Ag and Au into a vacuum arc melting furnace to be fedSmelting, wherein the smelting protective atmosphere is argon with the mass percent of 99.999%; the degree of vacuum was 5.3X 10^-3Pa, smelting current of 100A, smelting for 3min, and smelting for 15 times to prepare (Ni)_0.3Fe_0.3Co_0.2P_0.2)₉₆Ru_0.5Ir_0.5Rh_0.5Os_0.5Pt_{0. 5}Pd_0.5Ag_0.5Au_0.5A master alloy ingot;

thirdly, preparing an amorphous nanocrystalline alloy thin strip by a melt spinning method;

targeting (Ni) produced in step two_0.3Fe_0.3Co_0.2P_0.2)₉₆Ru_0.5Ir_0.5Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_0.5Au_0.5The mother alloy is mechanically crushed into small pieces and is preset in a quartz tube, the outlet width at the bottom of the quartz tube is 4mm, and the small pieces are put into a vacuum induction melting furnace of a rapid solidification device along with the quartz tube to ensure that the diameter is 6.7 multiplied by 10^-2Introducing 99.0 wt% argon gas under Pa of 0.05MPa, inducing current of coil to 8.2A, heating to melt completely, spraying onto copper wheel rotating at high speed under 0.02MPa and rotation speed of copper wheel of 21m/s to obtain (Ni)_0.3Fe_0.3Co_0.2P_0.2)₉₆Ru_0.5Ir_0.5Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_0.5Au_0.5An amorphous nanocrystalline alloy ribbon;

and (4) carrying out structural analysis on the sample prepared in the third step by using a Bruker AXS D8 type X-ray diffractometer, and adopting Ka rays of a copper target or a cobalt target. In the detection process, the scanning speed is 2 degrees/min, the scanning angle range is 20 degrees-80 degrees, the working voltage is 40kV, and the working current is 40 mA;

selectively corroding to prepare a nano porous structure;

step 41, using conductive adhesive to connect the copper wire and the (Ni) prepared in step three_0.3Fe_0.3Co_0.2P_0.2)₉₆Ru_0.5Ir_{0. 5}Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_0.5Au_0.5Fixedly connecting the amorphous nanocrystalline alloy thin strip, sealing the non-test part with non-conductive resin to expose (Ni)_0.3Fe_0.3Co_0.2P_0.2)₉₆Ru_0.5Ir_0.5Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_0.5Au_0.5The free surface of the amorphous nanocrystalline alloy ribbon;

step 42, adding (Ni)_0.3Fe_0.3Co_0.2P_0.2)₉₆Ru_0.5Ir_0.5Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_0.5Au_0.5The free surface of the amorphous nanocrystalline alloy thin strip is used as a working electrode, a graphite rod with the diameter of 3mm and the length of 100mm is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode;

43, adopting a three-electrode method, and selecting 0.3M H₃PO₄Performing constant potential corrosion on the solution at a corrosion potential of 0.25V (vs. SCE) for 25min at a corrosion temperature of 298K to obtain the (Ni) with the surface having the nano-porous structure_0.3Fe_0.3Co_0.2P_0.2)₉₆Ru_0.5Ir_0.5Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_0.5Au_0.5Amorphous gold thin strips;

step five, cleaning treatment;

the (Ni) with the surface having the nano-porous structure prepared in the fourth step_0.3Fe_0.3Co_0.2P_0.2)₉₆Ru_0.5Ir_0.5Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_0.5Au_0.5Washing the amorphous gold thin strip for 3 times by using deionized water, and then washing for 3 times by using absolute ethyl alcohol; placing into a vacuum drying oven, treating at 60 deg.C for 30min, cooling to room temperature, and taking out to obtain (Ni) with nano porous structure on surface_0.3Fe_0.3Co_0.2P_0.2)₉₆Ru_0.5Ir_0.5Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_0.5Au_0.5An oxygen evolution catalytic material.

Structural and performance characterization

The sample obtained in example 9 was subjected to structural analysis using an X-ray diffractometer.

The sample prepared in example 9 was observed with a JSM-7500F field emission scanning electron microscope.

The sample obtained in example 9 was analyzed by means of a photoelectron spectrometer model VG Scientific ESCALab220 i-XL. The excitation source is Al K alpha X-ray with power about 300W. The base vacuum during analysis was 3X 10^-9mbar. The electron binding energy was corrected for the C1s peak (284.8eV) of the contaminated carbon.

The cross section of the sample prepared in example 9 was observed with a JEOL JEM2010F transmission electron microscope

The sample prepared in example 9 was subjected to an electrochemical experiment at 298K using a Princeton Applied Research VersaSTAT 3 electrochemical workstation, a conventional three-electrode system was used, a graphite rod having a diameter of 3mm and a length of 100mm was used as an auxiliary electrode, a saturated calomel electrode was used as a reference electrode, a copper wire was fixedly connected to the non-test end of the corroded alloy ribbon using a conductive adhesive, the non-test end was sealed with a non-conductive resin, the free surface of the alloy ribbon was exposed, and the working electrode was used for an oxygen evolution performance test, the electrolyte was a 1mol/L KOH solution, and the scanning speed of the zeta potential polarization curve was 2 mV/s.

The test results showed that the NiFeCo-based composite doped with Ru, Ir, Os, Rh, Pt, Pd, Ag and Au prepared in example 9 was at 10mA/cm²The oxygen evolution geometric overpotential under current density is 178mV, the oxygen evolution reaction tower Phil slope is 30mV/dec, at 10 and 100mA/cm²The prepared NiFeCo-based composite material doped with Ru, Ir, Os, Rh, Pt, Pd, Ag and Au has excellent anodic oxygen evolution catalytic performance.

Example 10

With (Ni)_0.3Fe_0.3Co_0.2B_0.10P_0.05C_0.02Si_0.03)₉₅Ru₁Ir₁Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_0.5Au_0.5The preparation method of the target electrode by taking the amorphous nanocrystalline alloy thin strip as a precursor comprises the following steps:

step one, preparing target components;

according to (Ni)_0.3Fe_0.3Co_0.2B_0.10P_0.05C_0.02Si_0.03)₉₅Ru₁Ir₁Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_0.5Au_0.5Sequentially weighing single elements of Ni, Fe, Co, B, C, P, Si, Ru, Ir, Os, Rh, Pt, Pd, Ag and Au, wherein the purity of each element is not lower than 99.0%;

step two, preparing a master alloy;

step 21, smelting Fe and P in a vacuum induction smelting furnace in a smelting protective atmosphere of 99.999 percent by mass of argon and a vacuum degree of 3 multiplied by 10^-3Pa, smelting current of 80A for 6min to prepare a FeP pre-alloy ingot;

step 22, putting the FeP pre-alloy ingot and the elements of Ni, Co, B, C, Si, Ru, Ir, Os, Rh, Pt, Pd, Ag and Au into a vacuum arc melting furnace for melting, wherein the melting protective atmosphere is argon with the mass percentage of 99.999 percent; the degree of vacuum was 5.3X 10^-3Pa, smelting current of 115A, smelting for 3min, and smelting for 20 times to prepare (Ni)_0.3Fe_0.3Co_0.2B_0.10P_0.05C_0.02Si_{0. 03})₉₅Ru₁Ir₁Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_0.5Au_0.5A master alloy ingot;

thirdly, preparing an amorphous nanocrystalline alloy thin strip by a melt spinning method;

targeting (Ni) produced in step two_0.3Fe_0.3Co_0.2B_0.10P_0.05C_0.02Si_0.03)₉₅Ru₁Ir₁Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_0.5Au_0.5The mother alloy is mechanically crushed into small pieces and is preset in a quartz tube, the outlet width at the bottom of the quartz tube is 4mm, and the small pieces are put into a vacuum induction melting furnace of a rapid solidification device along with the quartz tube to ensure that the diameter is 6.9 multiplied by 10^-2Introducing 99.0 wt% argon gas of 0.05MPa below Pa, heating to melt completely, spraying onto copper wheel rotating at high speed at spraying pressure of 0.04MPa and rotation speed of 20m/s to obtain (Ni)_0.3Fe_0.3Co_0.2B_0.10P_0.05C_0.02Si_0.03)₉₅Ru₁Ir₁Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_0.5Au_0.5An amorphous nanocrystalline alloy ribbon;

and (4) carrying out structural analysis on the sample prepared in the third step by using a Bruker AXS D8 type X-ray diffractometer, and adopting Ka rays of a copper target or a cobalt target. In the detection process, the scanning speed is 2 degrees/min, the scanning angle range is 20 degrees-80 degrees, the working voltage is 40kV, and the working current is 40 mA;

selectively corroding to prepare a nano porous structure;

step 41, using conductive adhesive to connect the copper wire and the (Ni) prepared in step three_0.3Fe_0.3Co_0.2B_0.10P_0.05C_0.02Si_0.03)₉₅Ru₁Ir₁Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_0.5Au_0.5Fixedly connecting the amorphous nanocrystalline alloy thin strip, sealing the non-test part with non-conductive resin to expose (Ni)_0.3Fe_0.3Co_0.2B_0.10P_0.05C_0.02Si_0.03)₉₅Ru₁Ir₁Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_{0. 5}Au_0.5The free surface of the amorphous nanocrystalline alloy ribbon;

step 42, adding (Ni)_0.3Fe_0.3Co_0.2B_0.10P_0.05C_0.02Si_0.03)₉₅Ru₁Ir₁Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_0.5Au_0.5The free surface of the amorphous nanocrystalline alloy thin strip is used as a working electrode, a graphite rod with the diameter of 3mm and the length of 100mm is used as a counter electrode, and a Saturated Calomel Electrode (SCE) is used as a reference electrode;

43, adopting a three-electrode method, and selecting 0.3M H₃PO₄Performing constant potential corrosion on the solution at a corrosion potential of 0.3V (vs. SCE) for 25min at a corrosion temperature of 298K to obtain (Ni)_0.3Fe_0.3Co_0.2B_0.10P_0.05C_0.02Si_0.03)₉₅Ru₁Ir₁Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_0.5Au_0.5An amorphous alloy thin strip;

step five, cleaning treatment;

the (Ni) with the surface having the nano-porous structure prepared in the fourth step_0.3Fe_0.3Co_0.2B_0.10P_0.05C_0.02Si_0.03)₉₅Ru₁Ir₁Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_0.5Au_0.5Washing the amorphous alloy thin strip for 3 times by using deionized water, and then washing for 3 times by using absolute ethyl alcohol; placing into a vacuum drying oven, treating at 60 deg.C for 30min, cooling to room temperature, and taking out to obtain (Ni) with nano porous structure on surface_0.3Fe_0.3Co_0.2B_0.10P_0.05C_0.02Si_0.03)₉₅Ru₁Ir₁Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_0.5Au_0.5An oxygen evolution catalytic material.

Structural and performance characterization

The sample obtained in example 10 was subjected to structural analysis using an X-ray diffractometer.

The sample prepared in example 10 was observed with a JSM-7500F field emission scanning electron microscope.

Photoelectron spectroscopy of VG Scientific ESCALab220i-XL type is adoptedThe sample prepared in example 10 was analyzed. The excitation source is Al K alpha X-ray with power about 300W. The base vacuum during analysis was 3X 10^-9mbar. The electron binding energy was corrected for the C1s peak (284.8eV) of the contaminated carbon.

The cross section of the sample prepared in example 10 was observed with a JEOL JEM2010F transmission electron microscope

The sample prepared in the example 10 was subjected to an electrochemical experiment at 298K using a Princeton Applied Research VersaSTAT 3 electrochemical workstation, a conventional three-electrode system was used, a graphite rod having a diameter of 3mm and a length of 100mm was used as an auxiliary electrode, a saturated calomel electrode was used as a reference electrode, a copper wire was fixedly connected to the non-test end of the corroded alloy ribbon using a conductive adhesive, the non-test end was sealed with a non-conductive resin, the free surface of the alloy ribbon was exposed, and the working electrode was used for an oxygen evolution performance test, the electrolyte was a 1mol/L KOH solution, and the scanning speed of the zeta potential polarization curve was 2 mV/s.

The test results showed that the NiFeCo-based composite doped with Ru, Ir, Os, Rh, Pt, Pd, Ag and Au prepared in example 10 was at 10mA/cm²The oxygen evolution geometric overpotential under current density is 175mV, the oxygen evolution reaction tower Phil slope is 32mV/dec, at 10 and 100mA/cm²The prepared NiFeCo-based composite material doped with Ru, Ir, Os, Rh, Pt, Pd, Ag and Au has excellent anodic oxygen evolution catalytic performance.

Claims (7)

1. A method for preparing an integrated transition metal oxygen evolution catalytic material is characterized by comprising the following steps:

step one, preparing target components;

according to (Tm)_aNm_b)_xRm_yThe required elements are weighed in sequence, and the purity of each element is not lower than 99.9%; wherein:

tm is one or more of Fe, Ni and Co;

nm is one or more than one of P, C, Si and B;

rm is one or more of noble metals of Ru, Rh, Os, Ir, Pt, Pd, Ag and Au;

said (Tm)_aNm_b)_xRm_yThe atomic percentage of the dosage is x + y =100, x is more than or equal to 80 and less than or equal to 99.5; a + b =1, and a is more than or equal to 0.75 and less than or equal to 0.95;

step two, preparing a master alloy;

step one is weighed to be good (Tm)_aNm_b)_xRm_yMixing the target components, putting into a vacuum arc melting furnace, setting melting parameters, and melting to obtain (Tm)_aNm_b)_xRm_yThe amorphous nanocrystalline master alloy ingot of (a);

smelting parameters are as follows: the smelting protective atmosphere is argon with the mass percentage of 99.999 percent; vacuum degree of 1X 10^-4～8×10^-3Pa; the smelting current is 30-200A; smelting for 1-20 min, and smelting for 1-10 times;

thirdly, preparing an amorphous nanocrystalline alloy thin strip by a melt spinning method;

(Tm) obtained in the second step_aNm_b)_xRm_yThe amorphous nano-crystalline master alloy is mechanically crushed into small blocks and then is preset in a quartz tube, and is put into a vacuum induction melting furnace of a rapid solidification device along with the quartz tube; setting alloy strip parameter, to (Tm)_aNm_b)_xRm_yAfter completely melting, spraying the molten mixture on a copper wheel rotating at a high speed to prepare a product with a thickness (Tm) of 0.05-200 mu m_aNm_b)_xRm_yAn alloy thin strip;

preparing alloy thin strip parameters: the width of an outlet at the bottom of the quartz tube is 1-6 mm, and the smelting protective atmosphere is argon with the mass percent of 99.0%; vacuum degree of 6X 10^-2～2×10^-1Pa; the coil induction current is 2-20A; the injection pressure is 0.01-0.1 MPa; the rotation linear speed of the copper wheel is 15-50 m/s;

selectively corroding to prepare a nano porous structure;

step 41, using conductive adhesive to connect the copper wire and the (Tm) prepared in step three_aNm_b)_xRm_yOf thin strips of alloyThe non-test ends are fixedly connected and sealed with a non-conductive resin to expose (Tm)_aNm_b)_xRm_yA free surface of the alloy thin strip;

step 42, converting (Tm)_aNm_b)_xRm_yThe free surface of the alloy thin strip is used as a working electrode, a graphite rod with the diameter of 3mm and the length of 100mm is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode;

43, performing corrosion treatment in an acidic corrosion medium with the concentration of 0.001-5 mol/L by adopting a three-electrode method to obtain the nano porous structure (Tm) with the surface_aNm_b)_xRm_yA base amorphous alloy ribbon;

the corrosion potential is 0V-0.5V, vs. SCE, the corrosion time is 5 min-60 min, and the corrosion temperature is 298K;

step five, cleaning treatment;

the surface prepared in the fourth step has a nano porous structure (Tm)_aNm_b)_xRm_yCleaning the base amorphous alloy thin strip for 3-5 times by using deionized water, and then cleaning for 3-5 times by using absolute ethyl alcohol; then placing the mixture into a vacuum drying oven, treating the mixture for 15-45 min at the drying temperature of 60-80 ℃, cooling the mixture to room temperature, and taking out the cooled mixture to obtain the nano-porous material (Tm) with the surface having nano-pores_aNm_b)_xRm_yIs an oxygen evolution catalyst material and has a thickness of 0.05 to 200 μm;

prepared (Tm)_aNm_b)_xRm_yThe oxygen evolution catalytic material is composed of an alloy thin strip compounded by two layers of structures, wherein one layer is a nano porous structure with the surface doped with transition metal oxides or hydroxides and noble metals, and the other layer is a high-conductivity amorphous alloy matrix.

2. A method for preparing an integrated transition metal oxygen evolution catalytic material is characterized by comprising the following steps:

step one, preparing target components;

according to (Tm)_aNm_b)_xRm_yThe target components of (A) are sequentially weighed to obtain the required elementsAnd the purity of each element is not lower than 99.9%; wherein:

tm is one or more of Fe, Ni and Co;

nm is one or more than one of P, C, Si and B;

rm is one or more of noble metals of Ru, Rh, Os, Ir, Pt, Pd, Ag and Au;

said (Tm)_aNm_b)_xRm_yThe atomic percentage of the dosage is x + y =100, x is more than or equal to 80 and less than or equal to 99.5; a + b =1, and a is more than or equal to 0.75 and less than or equal to 0.95;

step two, preparing a master alloy;

for the alloy containing P element, firstly, mixing the simple substance of P element with one or more than one of Fe, Ni and Co;

then, the (Tm) will be weighed according to step one_aNm_b)_xRm_yMixing the target components, putting into a vacuum arc melting furnace, setting melting parameters, and melting to obtain (Tm)_aNm_b)_xRm_yThe amorphous nanocrystalline master alloy ingot of (a);

the smelting protective atmosphere is argon with the mass percent of 99.999 percent, and the vacuum degree is 3 multiplied by 10^-3Pa, smelting current of 80A for 6min to prepare a pre-alloy ingot; then putting the pre-alloy ingot and the rest elements into a vacuum arc melting furnace to be melted uniformly to obtain a master alloy ingot;

thirdly, preparing an amorphous nanocrystalline alloy thin strip by a melt spinning method;

(Tm) obtained in the second step_aNm_b)_xRm_yThe amorphous nano-crystalline master alloy is mechanically crushed into small blocks and then is preset in a quartz tube, and is put into a vacuum induction melting furnace of a rapid solidification device along with the quartz tube; setting alloy strip parameter, to (Tm)_aNm_b)_xRm_yAfter completely melting, spraying the molten mixture on a copper wheel rotating at a high speed to prepare a product with a thickness (Tm) of 0.05-200 mu m_aNm_b)_xRm_yAn alloy thin strip;

preparing alloy thin strip parameters: the outlet width at the bottom of the quartz tube is 1 to6mm, and the smelting protective atmosphere is argon with the mass percent of 99.0 percent; vacuum degree of 6X 10^-2～2×10^-1Pa; the coil induction current is 2-20A; the injection pressure is 0.01-0.1 MPa; the rotation linear speed of the copper wheel is 15-50 m/s;

selectively corroding to prepare a nano porous structure;

step 41, using conductive adhesive to connect the copper wire and the (Tm) prepared in step three_aNm_b)_xRm_yThe non-test ends of the thin alloy strip are fixedly connected and sealed with a non-conductive resin to expose (Tm)_aNm_b)_xRm_yA free surface of the alloy thin strip;

step 42, converting (Tm)_aNm_b)_xRm_yThe free surface of the alloy thin strip is used as a working electrode, a graphite rod with the diameter of 3mm and the length of 100mm is used as a counter electrode, and a saturated calomel electrode is used as a reference electrode;

43, performing corrosion treatment in an acidic corrosion medium with the concentration of 0.001-5 mol/L by adopting a three-electrode method to obtain the nano porous structure (Tm) with the surface_aNm_b)_xRm_yA base amorphous alloy ribbon;

the corrosion potential is 0V-0.5V, vs. SCE, the corrosion time is 5 min-60 min, and the corrosion temperature is 298K;

step five, cleaning treatment;

the surface prepared in the fourth step has a nano porous structure (Tm)_aNm_b)_xRm_yCleaning the base amorphous alloy thin strip for 3-5 times by using deionized water, and then cleaning for 3-5 times by using absolute ethyl alcohol; then placing the mixture into a vacuum drying oven, treating the mixture for 15-45 min at the drying temperature of 60-80 ℃, cooling the mixture to room temperature, and taking out the cooled mixture to obtain the nano-porous material (Tm) with the surface having nano-pores_aNm_b)_xRm_yIs an oxygen evolution catalyst material and has a thickness of 0.05 to 200 μm;

prepared (Tm)_aNm_b)_xRm_yThe oxygen-separating catalyst is an alloy thin band made up by compounding two layers of structures, one layer is an alloy thin band whose surface is doped with transition metal oxide or hydroxideThe nano porous structure of the object and the noble metal, and one layer is a high-conductivity amorphous alloy matrix.

3. The method for preparing an integrated transition metal-based oxygen evolution catalytic material according to claim 1 or 2, characterized in that: the prepared integrated transition metal oxygen evolution catalytic material comprises the following components:

(Ni_0.4Co_0.4P_0.2)₉₇Ru₃；

(Ni_0.4Fe_0.4B_0.2)₉₇Ru₃；

(Ni_0.4Fe_0.4B_0.2)₉₇Ru_1.5Ir_1.5；

(Ni_0.4Fe_0.4B_0.2)₉₇Ru_0.5Ir_0.5Rh_0.5Os_0.5Pt_0.5Pd_0.5；

(Fe_0.6Co_0.2P_0.2)₉₄Rh₁Os₁Ag₁Au₁Pt₁Pd₁；

(Fe_0.4Co_0.4B_0.1P_0.1)₉₇Ru_1.5Ir_1.5；

(Ni_0.4Co_0.4P_0.10C_0.05Si_0.05)₉₀Ru₅Ir₃Pt₁Pd₁；

(Ni_0.3Fe_0.3Co_0.2B_0.1P_0.1)₉₆Pt₁Pd₁Ag₁Au₁；

(Ni_0.3Fe_0.3Co_0.2P_0.2)₉₆Ru_0.5Ir_0.5Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_0.5Au_0.5；

or (Ni)_0.3Fe_0.3Co_0.2B_0.10P_0.05C_0.02Si_0.03)₉₅Ru₁Ir₁Rh_0.5Os_0.5Pt_0.5Pd_0.5Ag_0.5Au_0.5。

4. An integrated transition metal based oxygen evolution catalytic material prepared according to the method of any one of claims 1 to 3.

5. Use of an integrated transition metal based oxygen evolution catalytic material prepared according to the method of any of claims 1 to 3 or of the integrated transition metal based oxygen evolution catalytic material of claim 4, characterized in that: in a three-electrode system, will have a nanoporous (Tm)_aNm_b)_xRm_yThe oxygen evolution catalyst material is used as an anode electrode.

6. Use according to claim 5, characterized in that: prepared nanoporous (Tm)_aNm_b)_xRm_yThe oxygen evolution catalytic material is applied to the electrolyzed water.

7. Use according to claim 5, characterized in that: at 10mA/cm²The oxygen evolution geometric overpotential under the current density is 170-280 mV.

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