CN115491562A - Multi-principal-element porous alloy, preparation method thereof and porous electrode for electrolyzing seawater - Google Patents

Multi-principal-element porous alloy, preparation method thereof and porous electrode for electrolyzing seawater Download PDF

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CN115491562A
CN115491562A CN202211069673.3A CN202211069673A CN115491562A CN 115491562 A CN115491562 A CN 115491562A CN 202211069673 A CN202211069673 A CN 202211069673A CN 115491562 A CN115491562 A CN 115491562A
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刘雄军
李志斌
王辉
吴渊
吕昭平
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University of Science and Technology Beijing USTB
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Abstract

The invention relates to a multi-principal-element porous alloy, a preparation method thereof and a porous electrode for electrolyzing seawater. The preparation method of the multi-principal-element porous alloy comprises the following steps: obtaining Fe with nominal composition by smelting a Co b Ni c Nb d Ti e Ta f Hf g Zr h M x The alloy of (2) as a precursor; and selectively removing active phases in the alloy by a chemical/electrochemical dealloying method to prepare the multi-principal-element porous alloy. The multi-element porous alloy can be directly used as an electrode for electrolyzing seawater, the overpotentials of Oxygen Evolution (OER) and Hydrogen Evolution (HER) are 461 and 178mV respectively under the industrial electrolysis current density, and the OER stably works for more than 1600h under the current density. Has great application prospect in the aspect of an electrode device for producing hydrogen by electrolyzing seawater.

Description

Multi-principal-element porous alloy, preparation method thereof and porous electrode for electrolyzing seawater
Technical Field
The invention belongs to the field of clean and sustainable energy preparation and application, and particularly relates to a multi-principal-element porous alloy capable of being industrially produced and applied, a preparation method of the multi-principal-element porous alloy and a porous electrode for electrolyzing seawater.
Background
The hydrogen energy is regarded as a recognized green clean energy, has the characteristics of high efficiency, no pollution, easy storage and transportation and the like, and is known as a renewable energy source with development prospect most in the 21 st century. Among various hydrogen production technologies, the hydrogen production by water electrolysis has the advantages of high product purity, simple process, green and recyclable property, and the like, and is considered as the best way for leading to the hydrogen economy in the future. However, china has renewable ocean energy (offshore wind energy, wave energy, tidal current energy, island solar energy and the like) with huge reserves, wherein the ocean energy is coupled with the seawater electrolysis hydrogen production + hydrogen fuel cell to form an ideal energy circulation system capable of operating independently, and the energy self-sufficiency of facilities such as offshore civilian use, military use and the like can be realized. Renewable power generated by utilizing abandoned wind and abandoned light resources near the coastline is directly used for driving seawater to crack to produce hydrogen, so that renewable clean energy hydrogen can be produced, and the energy crisis is relieved; and fresh water resources can be effectively saved, crisis of water resources is relieved, and the method has great significance for promoting comprehensive and sustainable development of society.
Activity, stability and cost are three key factors to consider in designing electrocatalysts for practical applications. To date, most of the research on catalysts has focused on improving the catalytic activity of the catalyst and reducing the material cost. And only a few studies have systematically focused on improving the catalytic stability of the catalyst, particularly in alkaline seawater solutions. Although increasing the activity of low cost catalysts can reduce the energy consumption for the electrolysis of seawater, the stability of the catalyst may be a more important factor to consider in practical applications. This is because the energy consumption of a high activity, low stability catalyst increases dramatically with time compared to a high stability catalyst. While at present the stability of electrode catalysts based on seawater electrolysis remains a great challenge, a key problem is the very complex composition of seawater, where high concentrations of chloride ions accelerate the corrosion of the catalyst, which severely limits the long-term stability of the catalyst. In addition, chlorine ions can diffuse to the anode and compete with OER of the electrolyzed seawater, the OER reaction of the electrolyzed seawater is easier than the oxidation of the chlorine ions under an alkaline environment in a thermodynamic view, but the kinetics of the oxidation of the chlorine ions are more favorable than the OER reaction, because the oxidation of the chlorine ions is a 2-electron process and the OER reaction is a 4-electron process, so that the production of unnecessary chlorides by avoiding the oxidation of the chlorine ions also requires that the catalyst has excellent selectivity. Typical strategies for inhibiting chloride corrosion include: designing a catalyst for preferentially adsorbing the oxygen-containing intermediate, constructing a permeation selective layer, and adjusting an electrode structure to reject chloride ions and the like. However, these processes generally require complicated structural engineering and, to date, very few catalysts can be operated at commercial current densities for long periods of time. Therefore, the preparation of the electrolytic seawater catalyst which can be massively prepared, has high activity, high selectivity, high stability and functional structure integration has great challenge and significance.
Disclosure of Invention
The invention aims to overcome the problems that the high activity and the stability of the conventional electrolytic seawater catalytic material cannot be achieved at the same time and the defects that the traditional research catalyst cannot be prepared massively, and provides a preparation method of the electrolytic seawater electrode porous alloy material.
The technical scheme of the invention is as follows: a multi-principal element porous alloy having the chemical expression: fe a Co b Ni c Nb d Ti e Ta f Hf g Zr h M x M is one or more of Pt, ru, ir and Cu; wherein a is more than 0 and less than or equal to 55at percent, b is more than 0 and less than or equal to 55at percent, c is more than 0 and less than or equal to 55at percent, d is more than or equal to 0 and less than or equal to 55at percent, ande is not more than 55at%, f is not less than 0 but not more than 55at%, g is not less than 0 but not more than 55at%, h is not less than 0 but not more than 55at%, x is not less than 0 but not more than 5at%, and a + b + c + d + e + f + g + h + x =100at%.
Furthermore, the multi-primary porous alloy comprises a matrix, two layers of nano structures are arranged outside the matrix, and a porous structure is arranged between ligaments.
Further, the two layers of nanostructures are an intermediate layer and an outer layer; the substrate is an intermetallic compound, the middle layer is amorphous oxide, and the outer layer is multi-principal-element oxide.
Further, the amorphous oxide is (NbTiHfZrTa) Oy, and y is more than or equal to 40 and less than or equal to 80at%;
the multi-principal element oxide is (FeCoNiNbTiHfZrTaM) Oy, M is one or more of Pt, ru, ir and Cu, and y is more than or equal to 40 and less than or equal to 80at percent.
Another object of the present invention is to provide a method for preparing the above multi-element porous alloy, wherein the method specifically comprises the following steps:
s1) preparing a precursor alloy with controllable size;
and S2) placing the precursor alloy prepared in the step S1) in an acid solution for chemical/electrochemical dealloying, removing active phases, and reserving corrosion-resistant phases to form the multi-principal-element porous alloy with a porous and two-layer nano structure, wherein the pore diameter of the porous structure is 15-1000nm.
Further, the specific steps of S1) are as follows:
s1.1) putting metal raw materials into absolute ethyl alcohol, cleaning for multiple times in an ultrasonic mode, taking out the metal raw materials, and proportioning according to the designed nominal components of the alloy;
s1.2) smelting the weighed metal raw materials by adopting a vacuum arc furnace to prepare the precursor alloy with controllable size.
Further, the chemical/electrochemical dealloying method in S2) adopts 0.001-2 mol/L H as corrosive liquid 2 SO 4 、HNO 3 Or HCl solution, the corrosion temperature is 25-80 ℃, and the corrosion time is 1-72h.
The porous electrode for electrolyzing seawater is prepared from the multi-principal-element porous alloy obtained by the preparation method.
Furthermore, the porous electrode for electrolyzing seawater has unique self-repairing capability, can be directly used for electrolyzing water in an alkaline seawater electrolytic tank to produce hydrogen, and shows excellent electrocatalytic performance: at an industrial electrolytic current density (500 mA cm) -2 ) The lower oxygen evolution and hydrogen evolution overpotentials were 461 and 178mV, respectively, and the OER stability at this current density exceeded 1600h, and no performance decay and electrode corrosion were found in the stability test.
The invention has the following beneficial effects: the ligament of the multi-principal porous alloy electrode material prepared from the multi-principal porous alloy has a two-layer nano structure, the pore structure (15-1000 nm) can be accurately regulated and controlled by methods of physical metallurgy and preparation technology, the internal specific surface area is large, and the requirements on performance and stability under different working conditions can be met. Compared with the traditional foam Ni, the contact area of the active substance of the electrode material and the electrolyte is increased, and the electrocatalysis efficiency is improved.
The multi-element porous electrode prepared by the invention is a self-supporting structure, so that the problem of activity reduction caused by falling off due to poor conductivity and agglomeration of nano materials prepared by other methods is solved, the stability of the multi-element porous electrode is enhanced, and the electrocatalytic activity is greatly improved.
The prepared multi-element porous alloy electrode material has excellent seawater electrolysis selectivity, can avoid the competition between the oxidation of chloride ions and OER (Oxygen Evolution Reaction), and can prepare high-purity Oxygen.
The prepared electrode material has excellent corrosion resistance and excellent stability in seawater simulation liquid with harsh environment, so that the service life of the catalyst can be greatly prolonged, and the cost can be reduced. Meanwhile, an innovative idea of designing a catalyst is provided for the aspect of high-performance hydrogen production electrode materials for electrolyzing seawater, and the method has great application potential.
Drawings
FIG. 1 shows Fe using the process of the present invention 40-x Co 10 Ni 10 Nb 10 Ti 10 Zr 10 Hf 10 Pt x (x is more than or equal to 0 and less than or equal to 5 at%) of the alloy as a precursor, and the SE is removed from the alloy for 12hAnd (5) an M diagram.
FIG. 2 shows Fe using the method of the present invention 40-x Co 10 Ni 10 Nb 10 Ti 10 Zr 10 Hf 10 Ir x (x is more than or equal to 0 and less than or equal to 5 at%) as a precursor, and performing electrochemical dealloying for 12 h.
FIG. 3 shows Fe using the method of the present invention 40-x Co 10 Ni 10 Nb 10 Ti 10 Zr 10 Hf 10 Cu x (x is more than or equal to 0 and less than or equal to 5at percent) of the SEM image of the alloy precursor.
FIG. 4 shows Fe using the method of the present invention 40-x Co 10 Ni 10 Nb 10 Ti 10 Zr 10 Hf 10 Cu x (x is more than or equal to 0 and less than or equal to 5 at%) as a precursor, and taking the alloy as an SEM image after 12h of electrochemical dealloying.
FIG. 5 is a diagram of a nanoporous (FeCoNiPt) film using the method of the invention 2 TEM results of Nb electrodes are shown schematically.
FIG. 6 is a diagram of a nanoporous (FeCoNiIr) cell using the method of the invention 2 TEM results of Nb electrodes are shown schematically.
FIG. 7 is a nanoporous (FeCoNiPt) 2 Nb and nanoporous (FeCoNiIr) 2 And the polarization curve of the Nb electrode after conversion into the standard hydrogen electrode potential is shown schematically.
FIG. 8 is a nanoporous (FeCoNi) 2 A schematic diagram of a polarization curve of Nb measured in the simulated seawater solution and a corresponding taffy slope diagram, wherein a is a polarization curve diagram, and b is the taffy slope diagram.
FIG. 9 is a nanoporous (FeCoNi) 2 High current density (500 mA cm) of Nb electrode material in seawater simulation solution -2 ) The chronopotentiometric curve below is shown.
FIG. 10 shows Co 86 Nb 14 SEM image of the alloy after electrochemical dealloying for 12 h.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the accompanying drawings and embodiments.
The invention relates to a multi-principal-element porous alloy, which has the chemical expression as follows: fe a Co b Ni c Nb d Ti e Ta f Hf g Zr h M x M is one or more of Pt, ru, ir and Cu; wherein a is more than 0 and less than or equal to 55at percent, b is more than 0 and less than or equal to 55at percent, c is more than 0 and less than or equal to 55at percent, d is more than or equal to 0 and less than or equal to 55at percent, e is more than or equal to 0 and less than or equal to 55at percent, g is more than or equal to 0 and less than or equal to 55at percent, h is more than or equal to 0 and less than or equal to 55at percent, x is more than or equal to 0 and less than or equal to 5at percent, and a + b + c + d + e + f + g + h + x =100at percent.
The ligament of the multi-primary porous alloy has a two-layer nanostructure.
The two layers of nano structures are a substrate, a middle layer and an outer layer from inside to outside in sequence; the substrate is an intermetallic compound, the middle layer is amorphous oxide, and the outer layer is multi-principal-element oxide.
The amorphous oxide is (NbTiHfZrTa) Oy, and y is more than or equal to 40 and less than or equal to 80at percent;
the multi-principal element oxide is (FeCoNiNbTiHfZrTaM) Oy, M is one or more of Pt, ru, ir and Cu, and y is more than or equal to 40 and less than or equal to 80at percent.
The invention also provides a preparation method of the multi-principal-element porous alloy, which comprises the following steps:
s1) preparing a precursor alloy with controllable size;
and S2) placing the precursor alloy prepared in the step S1) in an acid solution for chemical/electrochemical dealloying, removing active phases, and reserving corrosion-resistant phases to form the multi-principal-element porous alloy with porous and two-layer nano structures, wherein the pore diameter of the porous structure is 15-1000nm.
Further, the specific steps of S1) are as follows:
s1.1) putting metal raw materials into absolute ethyl alcohol, cleaning for multiple times in an ultrasonic mode, taking out pure metal raw materials, and proportioning according to the designed nominal composition of the alloy;
s1.2) smelting the weighed metal raw materials by a vacuum arc furnace to prepare the precursor alloy with controllable size.
The chemical/electrochemical dealloying method in the S2) adopts 0.001 to 2mol/L of H as corrosive liquid 2 SO 4 、HNO 3 Or HCl solution, the corrosion temperature is 25-80 ℃, and the corrosion time is 1-72h.
The porous electrode for electrolyzing seawater is prepared from the multi-principal-element porous alloy obtained by the preparation method.
The porous electrode for electrolyzing seawater has unique self-repairing capability, can be directly used for electrolyzing water in an alkaline seawater electrolytic tank to prepare hydrogen, and shows excellent electrocatalytic performance: at an industrial electrolytic current density (500 mA cm) -2 ) The lower oxygen evolution and hydrogen evolution overpotentials were 461 and 178mV, respectively, and the OER stability at this current density exceeded 1600h, and no performance decay and electrode corrosion were found in the stability test.
Example 1:
with Fe 40-x Co 10 Ni 10 Nb 10 Ti 10 Zr 10 Hf 10 M x (M = Pt, ir, ru, cu, x is more than or equal to 0 and less than or equal to 5 at%) as the nominal component of the precursor alloy, weighing and proportioning the required elements, converting the pure elements ((Fe 99.99wt%, co 99.99wt%, ni 99.99wt%, cu 99.99wt%, nb 99.99wt%, ir 99.99wt%, ru 99.99wt% and Pt 99.99 wt%) required by the precursor alloy into mass according to the atomic percentage of the alloy, smelting to obtain the master alloy button ingot by adopting a high-purity argon atmosphere vacuum arc smelting method, smelting for 6-8 times to ensure that the components of the master alloy ingot are uniform, and then obtaining the precursor alloy with regular size by adopting a copper mold suction casting method
Example 2:
fe prepared in example 1 was used 40-x Co 10 Ni 10 Nb 10 Ti 10 Zr 10 Hf 10 Pt x (x is more than or equal to 0 and less than or equal to 5 at%) and 0.5mol L -1 H of (A) to (B) 2 SO 4 And (3) taking the aqueous solution as a corrosive solution, performing electrochemical dealloying, taking out after 12h, sequentially and repeatedly cleaning with ultrapure water and absolute alcohol to remove residual chemical substances in pores, and drying to prepare the porous electrode material.
FIG. 1 shows Fe 40-x Co 10 Ni 10 Nb 10 Ti 10 Zr 10 Hf 10 Pt x (x is more than or equal to 0 and less than or equal to 5 at%) alloyAnd (3) observing an SEM image after electrochemical dealloying for 12h to form a three-dimensional bicontinuous nano through hole structure, wherein the pore size is 50-100nm. a is x =1, b is x =2, c is x =3, d is x =4, e is x =5.
Example 3:
fe prepared in example 1 was used 40-x Co 10 Ni 10 Nb 10 Ti 10 Zr 10 Hf 10 Ir x (x is more than or equal to 0 and less than or equal to 5 at%) alloy as precursor, and H is 0.5mol/L 2 SO 4 And (3) taking the aqueous solution as an etching solution, performing electrochemical dealloying, taking out after 12h, sequentially washing with ultrapure water and absolute ethyl alcohol for multiple times to remove residual chemical substances in pores, and drying to obtain the porous electrode material.
FIG. 2 shows Fe 40-x Co 10 Ni 10 Nb 10 Ti 10 Zr 10 Hf 10 Ir x (x is more than or equal to 0 and less than or equal to 5 at%) in the SEM image of the alloy after 12h of electrochemical dealloying, a three-dimensional bicontinuous nano through hole structure can be observed, and the aperture size is 50-500nm. a is x =1, b is x =2, c is x =3, d is x =4, e is x =5.
Example 4:
fe prepared in example 1 was used 40-x Co 10 Ni 10 Nb 10 Ti 10 Zr 10 Hf 10 Cu x (x is more than or equal to 0 and less than or equal to 5 at%) and 0.5mol L -1 H of (A) to (B) 2 SO 4 And (3) taking the aqueous solution as a corrosive solution, performing electrochemical dealloying, taking out after 12h, sequentially and repeatedly cleaning with ultrapure water and absolute alcohol to remove residual chemical substances in pores, and drying to prepare the porous electrode material.
FIG. 3 shows Fe 40-x Co 10 Ni 10 Nb 10 Ti 10 Zr 10 Hf 10 Cu x (x is more than or equal to 0 and less than or equal to 5 at%) and is a typical eutectic structure. a is x =1, b is x =2, c is x =3, d is x =4.
FIG. 4 shows Fe 40-x Co 10 Ni 10 Nb 10 Ti 10 Zr 10 Hf 10 Cu x (x is more than or equal to 0 and less than or equal to 5 at%) in the SEM image of the alloy after 12h of electrochemical dealloying, a three-dimensional bicontinuous nano through hole structure can be observed, and the aperture size is 50-500nm. a is x =1, b is x =2, c is x =3, d is x =4.
Example 5:
the nano-porous electrode prepared in example 2 was subjected to microstructure characterization by transmission electron microscopy, and fig. 5 is Fe 37 Co 20 Ni 20 Nb 20 Pt 3 As a result of the transmission characterization after the dealloying, the electrode was observed to have a unique two-layer nanostructure, i.e., the outer layer was amorphous multicomponent oxide ((FeCoNiNbPt) Ox), the middle layer was amorphous NbOx, and the substrate was (FeCoNiPt) 2 Laves phase of Nb.
Example 6:
the microstructure of the nanoporous electrode prepared in example 3 was characterized by transmission electron microscopy, and fig. 6 is Fe 37 Co 20 Ni 20 Nb 20 Ir 3 As a result of the transmission characterization after the dealloying, the electrode has a unique two-layer nanostructure, i.e., the outer layer is amorphous multicomponent oxide ((FeCoNiNbIr) Ox), the middle layer is amorphous NbOx, and the matrix is (FeCoNiIr) 2 Laves phase of Nb. a is the result of energy spectrum line sweep, and b is the result of energy spectrum plane sweep.
Example 7:
we separately treated the electrochemically dealloyed Fe of example 1 40-x Co 20 Ni 20 Nb 20 Pt x (x =0,3 at%) porous electrode as working electrode, graphite electrode as auxiliary electrode, hg/HgO standard electrode as reference electrode to form three-electrode system, and the three-electrode system is in seawater simulation liquid (1 mol L) -1 KOH+0.5mol L -1 NaCL) at a sweep rate of 2mV/s -1 。
FIG. 7 shows the polarization curve of the porous electrode material after conversion into the standard hydrogen electrode potential, the electrode material with a small amount of noble metal added has greatly improved seawater hydrogen evolution performance and 500mA cm -2 The corresponding overpotential at the current density decreased from 429mV to 178mV.
Example 8:
we performed the electrochemical dealloying of Fe as in example 1 40 Co 20 Ni 20 Nb 20 The porous electrode is used as a working electrode, the graphite electrode is used as an auxiliary electrode, the Hg/HgO standard electrode is used as a reference electrode to form a three-electrode system, and the three-electrode system is arranged in seawater simulation liquid (1 mol L) -1 KOH+0.5mol L -1 NaCL) at a sweep rate of 2mV s -1 And simultaneously, a timing potential method is adopted for stability test.
FIG. 8a shows the polarization curve of the porous electrode material after conversion to the standard hydrogen electrode potential at an industrial current density of 500mA cm -2 The corresponding overpotential is only 461mV, which is lower than the oxidation potential of the chloride ions, thereby well avoiding the competition of the oxidation of the chloride ions and the OER.
FIG. 9 shows the porous electrode material at an industrial current density (500 mA cm) -2 ) The stability test of (2) can continuously work for more than 1600h, and the stability of the high-temperature-resistant material is very excellent.
Example 9:
by using Co 86 Nb 14 Alloy as precursor, 0.5mol L -1 H of (A) 2 SO 4 And (3) taking the aqueous solution as a corrosive solution, performing electrochemical dealloying, taking out after 12h, sequentially and repeatedly cleaning with ultrapure water and absolute alcohol to remove residual chemical substances in pores, and drying to prepare the porous electrode material.
FIG. 10 shows Co 86 Nb 14 And (3) observing an SEM image of the alloy after electrochemical dealloying for 12h to form a three-dimensional bicontinuous nano through hole structure.
The multi-principal element porous alloy, the preparation method thereof and the porous electrode for electrolyzing seawater are described in detail above. The above description of the embodiments is only for the purpose of helping to understand the method of the present application and its core ideas; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.
As used in the specification and claims, certain terms are used to refer to particular components. As one skilled in the art will appreciate, manufacturers may refer to a component by different names. The present specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. "substantially" means within an acceptable error range, and a person skilled in the art can solve the technical problem within a certain error range to substantially achieve the technical effect. The description which follows is a preferred embodiment of the present application, but is made for the purpose of illustrating the general principles of the application and not for the purpose of limiting the scope of the application. The scope of the present application is to be construed in accordance with the substance defined by the following claims.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a good or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such good or system. Without further limitation, an element defined by the phrases "comprising one of \8230;" does not exclude the presence of additional like elements in an article or system comprising the element.
It should be understood that the term "and/or" as used herein is merely one type of association that describes an associated object, meaning that three relationships may exist, e.g., a and/or B may mean: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter related objects are in an "or" relationship.
The foregoing description shows and describes several preferred embodiments of the present application, but as aforementioned, it is to be understood that the application is not limited to the forms disclosed herein, and is not to be construed as excluding other embodiments, but rather is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the application as expressed herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the application, which is to be protected by the claims appended hereto.

Claims (10)

1. A multi-principal element porous alloy is characterized in that the chemical expression of the multi-principal element porous alloy is as follows: fe a Co b Ni c Nb d Ti e Ta f Hf g Zr h M x M is one or more of Pt, ru, ir and Cu; wherein a is more than 0 and less than or equal to 55at percent, b is more than 0 and less than or equal to 55at percent, c is more than 0 and less than or equal to 55at percent, d is more than or equal to 0 and less than or equal to 55at percent, e is more than or equal to 0 and less than or equal to 55at percent, g is more than or equal to 0 and less than or equal to 55at percent, h is more than or equal to 0 and less than or equal to 55at percent, x is more than or equal to 0 and less than or equal to 5at percent, and a + b + c + d + e + f + g + h + x =100at percent.
2. The multi-element porous alloy of claim 1, wherein the ligament of the multi-element porous alloy comprises a matrix and two layers of nanostructures on the exterior of the matrix.
3. The multi-element porous alloy of claim 2, wherein the matrix is an intermetallic compound and the two layers of nanostructures are an intermediate layer and an outer layer; the middle layer is amorphous oxide, and the outer layer is multi-principal-element oxide.
4. The multi-element porous alloy of claim 3, wherein the amorphous oxide is (NbTiHfZrTa) Oy,40 ≦ y ≦ 80at%.
5. The multi-element porous alloy of claim 3, wherein the multi-element oxide is (FeCoNiNbTiHfZrTaM) Oy,40 ≦ y ≦ 80at%.
6. A method for preparing a multi-element porous alloy according to any one of claims 1 to 5, comprising the following steps:
s1) preparing a precursor alloy with controllable size;
and S2) placing the precursor alloy prepared in the step S1) in an acid solution for chemical/electrochemical dealloying, removing active phases, and retaining corrosion-resistant phases to form the multi-principal-element porous alloy with the porous structure, wherein the pore diameter of the porous structure is 15-1000nm.
7. The preparation method according to claim 6, wherein the specific steps of S1) are as follows:
s1.1) putting metal raw materials into absolute ethyl alcohol, cleaning for multiple times in an ultrasonic mode, taking out the metal raw materials, and proportioning according to the designed nominal components of the alloy;
s1.2) smelting the weighed metal raw materials by a vacuum arc furnace to prepare the precursor alloy with controllable size.
8. The method according to claim 6, wherein the chemical/electrochemical dealloying in S2) uses 0.001-2 mol/L H as etchant 2 SO 4 、HNO 3 Or HCl solution, the corrosion temperature is 25-80 ℃, and the corrosion time is 1-72h.
9. A porous electrode for electrolyzing seawater, characterized in that the porous electrode is prepared by the multi-principal-element porous alloy obtained by the preparation method according to any one of claims 6 to 8.
10. The porous electrode for electrolyzing seawater as recited in claim 9, wherein the porous electrode for electrolyzing seawater can be directly used for producing hydrogen by electrolyzing water in an alkaline seawater electrolyzer.
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