CN106609346B - A kind of amorphous alloy and its preparation method and application - Google Patents

Abstract

The invention relates to the field of catalysts, and discloses an amorphous alloy, a preparation method and application thereof. The chemical formula of the amorphous alloy is M _x A _y P _z , wherein, M is Pd and/or Pt; A is one of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and Mo One or more; x, y and z are mole fractions, and 1≤x≤60, 1≤y≤60, 1≤z≤40, x+y+z=100. The amorphous alloy provided by the invention can be used as a catalyst in the hydrogen evolution reaction, and has the advantages of high catalytic activity and good stability in an acidic system.

Description

A kind of amorphous alloy and its preparation method and application

technical field

The invention relates to the field of catalysts, in particular to an amorphous alloy and its preparation method and application.

Background technique

The storage, transportation and conversion of renewable energy (such as solar energy, wind energy, water potential energy, etc.) using hydrogen as a medium can achieve environmental friendliness and social sustainable development. At present, more than 95% of hydrogen comes from fossil fuels, and water is one of the important sources of hydrogen. The total energy of hydrogen extracted from it is 9000 times that of the earth's fossil fuel heat. Electrocatalytic water splitting via the hydrogen evolution reaction (HER) is an important process with high energy conversion efficiency. At present, the existing hydrogen evolution reaction catalysts are mainly based on noble metals such as platinum, but the limited reserves and high cost of platinum prevent the commercial application of this technology. MoS ₂ , Mo ₂ C, MoB, MoP, MoSe ₂ , WS ₂ and 3d transition metals were investigated as substituted Pt-based catalysts. In recent years, 3d transition metals, such as Fe, Co, Ni and their derivatives have attracted great attention as a substitute for Pt-based catalysts due to their high abundance and low cost, but these metals are susceptible to corrosion. For the hydrogen evolution reaction (HER) in acidic systems, the main challenge in replacing noble metal-based catalysts is the low efficiency and poor stability of non-noble metal catalysts.

Contents of the invention

The purpose of the present invention is to solve the problem of low catalytic activity and poor stability of hydrogen evolution reaction in acidic system, and provide an amorphous alloy and its preparation method and application.

In order to achieve the above object, the present invention provides an amorphous alloy, wherein the chemical formula of the amorphous alloy is M _x A _y P _z ;

Wherein, M is Pd and/or Pt; A is one or more of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and Mo;

x, y and z are mole fractions, and 1≤x≤60, 1≤y≤60, 1≤z≤40, x+y+z=100.

The present invention also provides a method for preparing the amorphous alloy, wherein the method comprises the following steps:

(1) melting metal M and metal A to obtain MA master alloy ingot;

(2) Induction melting the MA master alloy ingot with phosphorus to obtain a MAP master alloy; and

(3) The MAP master alloy and diboron trioxide are subjected to induction heating treatment, and then cooled.

Furthermore, the present invention also provides an amorphous alloy prepared by the above method.

In addition, the present invention also provides the application of the amorphous alloy in hydrogen evolution reaction.

The amorphous alloy provided by the invention can be used as a catalyst in the hydrogen evolution reaction, and has the advantages of high catalytic activity and good stability in an acidic system.

Other features and advantages of the present invention will be described in detail in the detailed description that follows.

Description of drawings

The accompanying drawings are used to provide a further understanding of the present invention, and constitute a part of the description, together with the following specific embodiments, are used to explain the present invention, but do not constitute a limitation to the present invention. In the attached picture:

Fig. 1 is the hydrogen evolution reaction polarization curve figure of embodiment 1 and comparative example 1;

Fig. 2 is the Tafel graph of embodiment 1 and comparative example 1;

Fig. 3 is the polarization curve figure after the different number of cycles of embodiment 1;

FIG. 4 is a chronoamperometry graph of Example 1 and Comparative Example 1.

Detailed ways

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

Neither the endpoints nor any values of the ranges disclosed herein are limited to such precise ranges or values, and these ranges or values are understood to include values approaching these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.

The present invention provides an amorphous alloy, wherein the chemical formula of the amorphous alloy is M _x A _y P _z ;

Wherein, M is Pd and/or Pt, preferably Pd; A is one or more of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and Mo;

Preferably, A is one or more of Fe, Co, Ni, Cu and Zn, preferably at least two of Fe, Co, Ni, Cu and Zn, more preferably Cu and selected from Fe, Co and A combination of at least one of Ni, most preferably a combination of Cu and Ni.

In a preferred embodiment, M is Pd, and A is a combination of Cu and Ni.

In the present invention, x, y and z are mole fractions, and 1≤x≤60, 1≤y≤60, 1≤z≤40, x+y+z=100; preferably, 25≤x≤50, 25 ≤y≤50, 10≤z≤30; more preferably, 35≤x≤45, 35≤y≤45, 15≤z≤25; most preferably, x=40, y=40, z=20 .

In the present invention, the structure of the amorphous alloy is not particularly limited, and may be a conventional structure in the art, such as strips, films, mesoporous materials, one-dimensional nanowire arrays or one-dimensional nanotube arrays, preferably Tape or film, more preferably tape.

The present invention also provides a method for preparing the amorphous alloy, wherein the method comprises the following steps:

(1) melting metal M and metal A to obtain MA master alloy ingot;

(2) Induction melting the MA master alloy ingot with phosphorus to obtain a MAP master alloy; and

(3) The MAP master alloy and diboron trioxide are subjected to induction heating treatment, and then cooled.

According to a preferred embodiment of the present invention, the smelting process in step (1) includes: first evacuating the smelting chamber to a vacuum degree below 10Pa (such as 8Pa, 5Pa, 3Pa, 1Pa or 0.5Pa) with a mechanical pump, Then use a molecular pump to evacuate the melting chamber to below 3×10 ^-3 Pa (such as 3×10 ^-3 Pa, 1×10 ^-3 Pa, 7×10 ^-4 Pa, 3×10 ^-4 Pa, 5×10 ^-6 Pa or 1×10 ^-7 Pa), and then filled with inert gas, and then the raw material metal M and metal A are smelted in the smelting chamber. The melting process may be carried out in an electric arc melting furnace. The arc melting furnace may use tungsten electrodes.

According to a preferred embodiment of the present invention, in order to absorb oxygen and other impurities in the smelting chamber, the smelting process in step (1) preferably further includes: before injecting raw material M and metal A and after filling inert gas, Inject sponge titanium for smelting.

In the present invention, the amount of titanium sponge is not particularly limited, as long as the amount of titanium sponge can completely absorb oxygen and other impurities in the smelting chamber. Preferably, the titanium sponge is used in an amount of 10-20 parts by weight, more preferably 14-16 parts by weight, based on 100 parts by weight of the total weight of the raw material metal M and metal A.

In the present invention, in order to ensure uniform smelting, the smelting process in step (1) can be repeated 2-7 times, preferably 3-5 times.

In the present invention, in the induction smelting process of step (2), since phosphorus is volatile, preferably, the amount of phosphorus used is 1.01-1.7 times, preferably 1.1-1.4 times, the theoretical molar equivalent.

In the present invention, the induction melting process of step (2) can be carried out in a quartz glass tube under vacuum conditions; preferably, the vacuum degree of the vacuum conditions is 2×10 ^-3 -4×10 ^-3 Pa .

In step (2), after the induction melting process is finished, the mass of the obtained MAP master alloy is weighed, and the mass of the MA master alloy ingot is subtracted from the mass of the MAP master alloy to obtain the MAP The actual phosphorous mass of the master alloy. If the quality of phosphorus is too high, a certain amount of the MA master alloy ingot is added according to the proportion and the induction melting is continued until the MAP master alloy with a suitable phosphorus content is obtained.

In the present invention, in the induction heating treatment of step (3), there is no particular limitation on the amount of diboron trioxide used, but in order to improve the forming ability of amorphous glass, preferably, the boron trioxide The volume ratio of the amount of diboron to the MAP master alloy is 1.5-2.5:1, more preferably 1.5-2.3:1, further preferably 1.6-2:1.

In the present invention, the process of the induction heating treatment in step (3) may include: putting the MAP master alloy and diboron trioxide into a quartz tube, and evacuating the quartz tube to below 10 ^-5 Pa (such as 10 ^-6 Pa, 10 ^-7 Pa, 10 ^-8 Pa or 10 ^-9 Pa), filled with an inert gas and sealed, and then the sealed quartz tube was subjected to induction heating in a high-vacuum single-roller strip furnace. The high vacuum here refers to a vacuum degree of 6×10 ^-4 Pa or less.

In the present invention, the method may further include: heating the MAP master alloy obtained after the treatment in step (3) to melt, and then spraying it onto the substrate to obtain an amorphous alloy ribbon. Wherein, the heating process can be implemented by a conventional method in the art, for example, it can be induced current heating.

In a preferred embodiment of the present invention, the MAP master alloy is placed in a quartz tube, the quartz tube is placed in the induction coil of a high-vacuum single-roller strip furnace, and the height of the quartz tube is adjusted to make it The distance between the nozzle and the copper roller is 2-3mm, and the vacuum degree in the belt throwing furnace is evacuated to below 4×10 ^-4 Pa (such as 1×10 ^-4 Pa, 4×10 ^-5 Pa, 3×10 ^-6 Pa or 1×10 ^-7 Pa), fill high-purity argon gas (purity ≥ 99.999%) to the pressure of 0.05-0.08 MPa in the belt throwing furnace, and use induction current to heat the MAP master alloy to melt state, which is sprayed onto a rotating copper roll to obtain an amorphous alloy ribbon. Wherein, the rotational speed of the copper roller is 10-50m/s.

In the present invention, the degree of vacuum refers to the degree of absolute vacuum.

Furthermore, the present invention also provides an amorphous alloy prepared by the method of the present invention.

In addition, the present invention also provides the application of the amorphous alloy in hydrogen evolution reaction. The amorphous alloy provided by the invention can be used as a catalyst in the hydrogen evolution reaction, and has high catalytic activity and stability in an acidic system.

The present invention will be described in detail below by way of examples. In the following examples, the electrochemical testing method of the amorphous alloy strip is as follows:

(1) Pretreatment of the amorphous alloy ribbon. Polish the surface of the amorphous alloy strip with sandpaper to remove impurities and oxide films, alternately wash five times with 0.5mol/L sulfuric acid and deionized water, then alternately wash five times with 1mol/L KOH solution and deionized water, dry and set aside;

(2) Electrochemical test. The catalytic activity and stability were characterized by a typical three-electrode test system. Get the amorphous alloy strip that area is 0.5cm ² step (1) process as working electrode, the Pt sheet that area is 1cm ² is as counter electrode, Ag/AgCl electrode is as reference electrode (potential expression mode is E vs RHE= E vs Ag/AgCl+0.059×pH+0.204V, RHE is a reversible hydrogen reference electrode). The electrolyte is 0.5mol/L sulfuric acid. Before the test, first put the working electrode in 0.5mol/L sulfuric acid solution, at a scanning speed of 100mV/s, and the voltage range is 0-1.2V vs RHE, and activate it for 10 circles by cyclic voltammetry (CV) to activate the electrode and Remove surface adsorbed impurities.

Hydrogen evolution reaction catalytic activity test: the linear sweep (LSV) method was adopted, the sweep speed was 2mV/s, and the voltage range was 0.1V-–0.6V vs RHE.

Hydrogen evolution reaction stability test: Two methods were used: cyclic voltammetry (CV) and chronoamperometry (CA). The CA test adopts the above three-electrode system, the test voltage is 0.3V vs RHE, and the test time is 50000s; the CV test condition is that the voltage range is 0.1V-–0.3V vs RHE, the scanning speed is 100mV/s, and 1000 cycles and 10000 cycles are respectively taken. After the catalyst was tested its linear sweep polarization curve.

In the following examples, Pd, Pt, Cu, Ni, P, Co and Fe were purchased from Beijing Cuibolin Nonferrous Metal Technology Development Center Co., Ltd.; in the comparative examples, 10wt% Pt/C material was purchased from Alfa Aisha (China ) Chemical Co., Ltd.

Example 1

This example is used to illustrate the preparation method of the amorphous alloy Pd ₄₀ Cu ₃₀ Ni ₁₀ P ₂₀ .

Mix Pd, Cu, and Ni with a purity greater than 99.9% in a ratio of 40:30:10, with a total mass of 20 grams. First use a mechanical pump to pump the vacuum of the electric arc furnace melting chamber to 10Pa, then use a molecular pump to pump it to 1x10 ^-3 Pa, then fill it with high-purity argon, put 2g of titanium sponge into the melting chamber for melting, and then put Pd, Cu The mixture with Ni is melted three times in an electric arc furnace to obtain a PdCuNi master alloy ingot.

Weigh the quality of the obtained PdCuNi master alloy ingot, calculate the mass of phosphorus required according to the composition ratio of Pd ₄₀ Cu ₃₀ Ni ₁₀ P ₂₀ , weigh the phosphorus with a mass of 1.2 times the theoretical value, and seal it together with the PdNiCu master alloy ingot Induction melting was carried out in a quartz glass tube with a vacuum degree of 2×10 ^-3 Pa to obtain a Pd ₄₀ Cu ₃₀ Ni ₁₀ P ₂₀ master alloy.

Put the Pd ₄₀ Cu ₃₀ Ni ₁₀ P ₂₀ master alloy obtained above and diboron trioxide twice the volume of the Pd ₄₀ Cu ₃₀ Ni ₁₀ P ₂₀ master alloy into a quartz tube, evacuate to 10 ^-5 Pa, and fill with After high-purity argon gas, the quartz tube is sealed, and the sealed quartz tube is induction-heated in a vacuum single-roller strip furnace. After cooling, the Pd ₄₀ Cu ₃₀ Ni ₁₀ P ₂₀ alloy is taken out.

Put the Pd ₄₀ Cu ₃₀ Ni ₁₀ P ₂₀ alloy into the quartz tube, and place it in the induction coil of the strip furnace, adjust the height of the quartz tube so that the distance between the nozzle and the copper roller is 2mm, and reduce the vacuum degree in the strip furnace to Pump to 4x10 ^-4 Pa, fill the furnace with high-purity argon until the furnace pressure is 0.06MPa, use induction current to heat the Pd ₄₀ Cu ₃₀ Ni ₁₀ P ₂₀ alloy to a molten state, and then spray it to the copper at a speed of 10m/s On the roll, the Pd ₄₀ Cu ₃₀ Ni ₁₀ P ₂₀ amorphous alloy strip is obtained.

The catalytic activity and stability of the obtained Pd ₄₀ Cu ₃₀ Ni ₁₀ P ₂₀ amorphous alloy ribbons in the hydrogen evolution reaction were tested by electrochemical testing methods. The catalytic activity results are shown in Table 1 and Figure 1-2, and the stability results are shown in Table 1. 1 and Figure 3-4.

Comparative example 1

This comparative example is used to illustrate the catalytic activity and stability of 10wt% Pt/C material in the hydrogen evolution electrocatalytic reaction.

The catalytic activity and stability of commercial 10wt% Pt/C materials in the hydrogen evolution reaction were tested by electrochemical testing method. The catalytic activity results are shown in Table 1 and Figure 1-2, and the stability results are shown in Table 1 and Figure 4.

Example 2

This example is used to illustrate the preparation method of the amorphous alloy Pd ₃₅ Cu ₂₅ Ni ₂₀ P ₂₀ .

Mix Pd, Cu, and Ni with a purity greater than 99.9% in a ratio of 35:25:20, with a total mass of 20 grams. First use a mechanical pump to pump the vacuum of the electric arc furnace melting chamber to 8Pa, then use a molecular pump to pump it to 3x10 ^-3 Pa, then fill it with high-purity argon, put 4g of titanium sponge into the melting chamber for melting, and then put Pd, Cu The mixture with Ni was melted in an electric arc furnace for 5 times to obtain a PdCuNi master alloy ingot.

Weigh the quality of the obtained PdCuNi master alloy ingot, calculate the mass of phosphorus required according to the composition ratio of Pd ₃₅ Cu ₂₅ Ni ₂₀ P ₂₀ , weigh the phosphorus with a mass of 1.4 times the theoretical value, and seal it together with the PdNiCu master alloy ingot Induction melting is carried out in a quartz glass tube with a vacuum degree of 4×10 ^-3 Pa to obtain a Pd ₃₅ Cu ₂₅ Ni ₂₀ P ₂₀ master alloy.

Put the Pd ₃₅ Cu ₂₅ Ni ₂₀ P ₂₀ master alloy obtained above and diboron trioxide whose volume is 1.6 times that of the Pd ₃₅ Cu ₂₅ Ni ₂₀ P ₂₀ master alloy together into a quartz tube, evacuate to 10 ^-6 Pa, and fill with After high-purity argon gas, the quartz tube is sealed, and the sealed quartz tube is induction-heated in a vacuum single-roller strip furnace, and the Pd ₃₅ Cu ₂₅ Ni ₂₀ P ₂₀ alloy is taken out after cooling.

Put the Pd ₃₅ Cu ₂₅ Ni ₂₀ P ₂₀ alloy into the quartz tube and place it in the induction coil of the strip furnace. To 1x10 ^-4 Pa, fill the furnace with high-purity argon to a pressure of 0.08MPa, use induction current to heat the Pd ₃₅ Cu ₂₅ Ni ₂₀ P ₂₀ alloy to a molten state, and then spray it to a copper roller with a speed of 50m/s On, the Pd ₃₅ Cu ₂₅ Ni ₂₀ P ₂₀ amorphous alloy ribbon is obtained.

The catalytic activity and stability of the obtained Pd ₃₅ Cu ₂₅ Ni ₂₀ P ₂₀ amorphous alloy ribbons in the hydrogen evolution reaction were tested by electrochemical testing method, and the results are shown in Table 1.

Example 3

This example is used to illustrate the preparation method of the amorphous alloy Pd ₄₀ Cu ₂₀ Ni ₁₅ P ₂₅ .

Mix Pd, Cu, and Ni with a purity greater than 99.9% in a ratio of 40:20:15, with a total mass of 20 grams. First use a mechanical pump to pump the vacuum of the electric arc furnace melting chamber to 5Pa, then use a molecular pump to pump it to 3x10 ^-4 Pa, then fill it with high-purity argon, put 4g of titanium sponge into the melting chamber for melting, and then put Pd, Cu The mixture with Ni is put into an electric arc furnace and smelted 4 times to obtain a PdCuNi master alloy ingot.

Weigh the quality of the obtained PdCuNi master alloy ingot, calculate the mass of phosphorus required according to the composition ratio of Pd ₄₀ Cu ₂₀ Ni ₁₅ P ₂₅ , weigh the phosphorus with a mass of 1.1 times the theoretical value, and seal it together with the PdNiCu master alloy ingot Induction melting is carried out in a quartz glass tube with a vacuum degree of 3×10 ^-3 Pa to obtain a Pd ₄₀ Cu ₂₀ Ni ₁₅ P ₂₅ master alloy.

Put the Pd ₄₀ Cu ₂₀ Ni ₁₅ P ₂₅ master alloy obtained above and diboron trioxide whose volume is 1.8 times that of the Pd ₄₀ Cu ₂₀ Ni ₁₅ P ₂₅ master alloy into a quartz tube, evacuate to 10 ^-5 Pa, and fill with After high-purity argon gas, the quartz tube is sealed, and the sealed quartz tube is induction-heated in a vacuum single-roller strip furnace. After cooling, the Pd ₄₀ Cu ₂₀ Ni ₁₅ P ₂₅ alloy is taken out.

Put the Pd ₄₀ Cu ₂₀ Ni ₁₅ P ₂₅ alloy into the quartz tube, and place it in the induction coil of the strip furnace, adjust the height of the quartz tube so that the distance between the nozzle and the copper roller is 2mm, and pump out the vacuum in the strip furnace To 4x10 ^-5 Pa, fill the furnace with high-purity argon to a pressure of 0.05MPa, use induction current to heat the Pd ₄₀ Cu ₂₀ Ni ₁₅ P ₂₅ alloy to a molten state, and then spray it to a copper roller with a speed of 30m/s On, the Pd ₄₀ Cu ₂₀ Ni ₁₅ P ₂₅ amorphous alloy ribbon is obtained.

The catalytic activity and stability of the obtained Pd ₄₀ Cu ₂₀ Ni ₁₅ P ₂₅ amorphous alloy ribbons in the hydrogen evolution reaction were tested by electrochemical testing method, and the results are shown in Table 1.

Example 4

This example is used to illustrate the preparation method of the amorphous alloy Pd ₄₀ Co ₃₀ Fe ₁₀ P ₂₀ .

Pd ₄₀ Cu ₃₀ Fe ₁₀ P ₂₀ was prepared according to the method of Example 1, except that Pd, Co, and Fe with a purity greater than 99.9% were mixed in a ratio of 40:30:10, and the total mass was 20 grams.

The catalytic activity and stability of the obtained Pd ₄₀ Cu ₃₀ Fe ₁₀ P ₂₀ amorphous alloy ribbons in the hydrogen evolution reaction were tested by electrochemical testing method, and the results are shown in Table 1.

Example 5

This example is used to illustrate the preparation method of the amorphous alloy Pd ₃₅ Co ₂₅ Fe ₂₀ P ₂₀ .

Pd ₃₅ Co ₂₅ Fe ₂₀ P ₂₀ was prepared according to the method of Example 2, except that Pd, Co, and Fe with a purity greater than 99.9% were mixed in a ratio of 35:25:20, and the total mass was 20 grams.

The catalytic activity and stability of the obtained Pd ₃₅ Co ₂₅ Fe ₂₀ P ₂₀ amorphous alloy ribbons in the hydrogen evolution reaction were tested by electrochemical testing method, and the results are shown in Table 1.

Example 6

This example is used to illustrate the preparation method of the amorphous alloy Pd ₄₀ Co ₂₀ Fe ₁₅ P ₂₅ .

Pd ₄₀ Co ₂₀ Fe ₁₅ P ₂₅ was prepared according to the method of Example 3, except that Pd, Co, and Fe with a purity greater than 99.9% were mixed in a ratio of 40:20:15, and the total mass was 20 grams.

The catalytic activity and stability of the obtained Pd ₄₀ Co ₂₀ Fe ₁₅ P ₂₅ amorphous alloy ribbons in the hydrogen evolution reaction were tested by electrochemical testing method, and the results are shown in Table 1.

Example 7

This example is used to illustrate the preparation method of the amorphous alloy Pt ₄₀ Cu ₄₀ P ₂₀ .

Pt ₄₀ Cu ₄₀ P ₂₀ was prepared according to the method of Example 1, except that Pt and Cu with a purity greater than 99.9% were mixed in a ratio of 1:1, and the total mass was 20 grams.

The catalytic activity and stability of the obtained Pt ₄₀ Cu ₄₀ P ₂₀ amorphous alloy ribbons in the hydrogen evolution reaction were tested by electrochemical testing method, and the results are shown in Table 1.

Example 8

This example is used to illustrate the preparation method of the amorphous alloy Pt ₃₅ Cu ₄₅ P ₂₀ .

Pt ₃₅ Cu ₄₅ P ₂₀ was prepared according to the method of Example 2, except that Pt and Cu with a purity greater than 99.9% were mixed in a ratio of 35:45, and the total mass was 20 grams.

The catalytic activity and stability of the obtained Pt ₃₅ Cu ₄₅ P ₂₀ amorphous alloy ribbons in the hydrogen evolution reaction were tested by electrochemical testing method, and the results are shown in Table 1.

Example 9

This example is used to illustrate the preparation method of the amorphous alloy Pt ₄₀ Cu ₃₅ P ₂₅ .

Pt ₄₀ Cu ₃₅ P ₂₅ was prepared according to the method of Example 3, except that Pt and Cu with a purity greater than 99.9% were mixed in a ratio of 40:35, and the total mass was 20 grams.

The catalytic activity and stability of the obtained Pt ₄₀ Cu ₃₅ P ₂₅ amorphous alloy ribbons in the hydrogen evolution reaction were tested by electrochemical testing method, and the results are shown in Table 1.

Table 1

Note: Current retention rate after 50000 seconds test = current density after 50000 seconds test / test initial current density.

As can be seen from the data in Figures 1-2 and Table 1, the voltage and Tafel slope corresponding to the current density of the amorphous alloy provided by the present invention is -1.0mA/cm ² and the commercial Pt/C catalyst is equivalent, 50000 After the second test, it has a high current retention rate, and, as can be seen from Figure 3-4, the cyclic voltammetry curve after scanning 1000 cycles and 10000 cycles by cyclic voltammetry has not changed significantly. Therefore, the amorphous alloy provided by the invention has high catalytic activity and stability in hydrogen evolution reaction. The invention solves the problems of low catalyst activity and poor stability of the hydrogen evolution reaction in an acidic system.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way if there is no contradiction. The combination method will not be described separately.

In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (19)

1. An amorphous alloy, characterized in that the chemical formula of the amorphous alloy is M _x A _y P _z ; Wherein, M is Pd and/or Pt; A is one or more of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn and Mo; x, y and z are mole fractions, and 35≤x<45, 35≤y≤45, 15≤z≤25, x+y+z=100. 2. The amorphous alloy according to claim 1, wherein M is Pd. 3. The amorphous alloy according to claim 1 or 2, wherein A is one or more of Fe, Co, Ni, Cu and Zn. 4. The amorphous alloy according to claim 3, wherein A is at least two of Fe, Co, Ni, Cu and Zn. 5. The amorphous alloy according to claim 4, wherein A is a combination of Cu and at least one selected from Fe, Co and Ni. 6. The amorphous alloy according to claim 5, wherein A is a combination of Cu and Ni. 7. The amorphous alloy according to any one of claims 1, 2 and 4-6, wherein the structure of the amorphous alloy is strip material, thin film, mesoporous material, one-dimensional nanowire array or one-dimensional array of nanotubes. 8. A method for preparing the amorphous alloy described in any one of claims 1-7, wherein the method may further comprise the steps: (1) melting metal M and metal A to obtain MA master alloy ingot; (2) Induction melting the MA master alloy ingot with phosphorus to obtain a MAP master alloy; and (3) The MAP master alloy and diboron trioxide are subjected to induction heating treatment, and then cooled. 9. The method according to claim 8, wherein the smelting process of step (1) is repeated for 2-7 times. 10. The method according to claim 9, wherein the smelting process of step (1) is repeated for 3-5 times. 11. The method according to claim 8, wherein, in the induction melting process of step (2), the amount of phosphorus used is 1.01-1.7 times of the theoretical molar equivalent. 12. The method according to claim 11, wherein, in the induction melting process of step (2), the amount of phosphorus used is 1.1-1.4 times of the theoretical molar equivalent. 13. The method according to any one of claims 8, 11 and 12, wherein the induction melting process of step (2) is carried out in a quartz glass tube under vacuum conditions. 14. The method according to claim 13, wherein the vacuum degree of the vacuum condition is 2×10 ⁻³ to 4×10 ⁻³ Pa. 15. The method according to claim 8, wherein, in the induction heating treatment in step (3), the volume ratio of the amount of diboron trioxide to the MAP master alloy is 1.5-2.5:1. 16. The method according to claim 8 or 15, wherein the process of the induction heat treatment of step (3) comprises: putting the MAP master alloy and diboron trioxide into a quartz tube, pumping the quartz tube The vacuum is below 10 ^-5 Pa, filled with inert gas and sealed, and then the sealed quartz tube is subjected to induction heating treatment in a high-vacuum single-roller strip furnace. 17. The method according to any one of claims 8-12, 14 and 15, wherein the method further comprises: heating the MAP master alloy obtained after the treatment in step (3) to melting, and then spraying it onto the substrate , to obtain amorphous alloy strips. 18. Amorphous alloy prepared by the method of any one of claims 8-17. 19. The application of the amorphous alloy according to any one of claims 1-7 and 18 in hydrogen evolution reaction.