CN116334660A - Amorphous composite material electrolyzed water catalyst and preparation method thereof - Google Patents

Amorphous composite material electrolyzed water catalyst and preparation method thereof Download PDF

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CN116334660A
CN116334660A CN202310284133.5A CN202310284133A CN116334660A CN 116334660 A CN116334660 A CN 116334660A CN 202310284133 A CN202310284133 A CN 202310284133A CN 116334660 A CN116334660 A CN 116334660A
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amorphous composite
composite material
amorphous
electrolyzed water
catalyst
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姜思达
李博
梁维中
宁志良
崔艺凡
王泳惠
闻漫兮
狄婧
孙剑飞
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Harbin Institute of Technology
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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Abstract

The invention discloses an amorphous composite material water electrolysis catalyst and a preparation method thereof, and aims to solve the problems that the existing OER catalyst contains noble metals, has high cost and has catalytic activity to be improved. The preparation method comprises the following steps: 1. according to Fe 38～42 Ni 36～40 Mo 0～5 B 16～20 Weighing iron, nickel, molybdenum and boron simple substances as raw materials in a chemical formula, and smelting the raw materials to obtain a master alloy ingot; 2. carrying out suction casting on the master alloy ingot by adopting a water-cooling copper mold suction casting method; 3. placing the alloy rod into a crucible, preheating a copper wheel by using a baking lamp, starting the copper wheel to rotate, and treating the alloy rod by adopting a melt pulling method; 4. dealloying treatment. The microstructure of the amorphous composite material electrolyzed water catalyst of the invention is that nano crystals are uniformly distributed on an amorphous matrix, the morphology is surface porous metal microfilaments with the diameter of 35-50 mu m, and the catalytic activity is improvedHigh current density of 10mAcm ‑2 The overpotential at this time was only 233mV at the minimum.

Description

Amorphous composite material electrolyzed water catalyst and preparation method thereof
Technical Field
The invention relates to an amorphous composite catalyst and a preparation method thereof, in particular to an amorphous composite alkaline electrolysis water oxygen evolution reactant and a preparation method thereof.
Background
In recent years, water electrolysis hydrogen production technology has received a great deal of attention. People utilize electric power which is difficult to be connected with water, electricity and the like to prepare hydrogen through electrolysis water reaction, the heat quantity of the hydrogen is high, the hydrogen is easy to store, and combustion products are only water and are very friendly to the environment, so that the electrolysis water technology becomes one of the most promising technologies for solving the current environmental and energy problems. However, the electrolyzed water reaction is an involuntary upward reaction, and a catalyst is required to reduce the overpotential and improve the reaction efficiency. The electrolytic water is divided into two half reactions, one is a Hydrogen Evolution Reaction (HER) that generates hydrogen at the cathode and the other is an Oxygen Evolution Reaction (OER) that generates oxygen at the anode. The OER process is a four-electron transfer process, has more intermediate products, very complex mechanism, slow reaction kinetics and high overpotential, and is a key factor for limiting the water electrolysis efficiency. The OER catalysts currently commercialized are platinum group noble metal catalysts, such as IrO 2 And RuO (Ruo) 2 Expensive, the crust reserves are rare, which greatly limits the industrial application of the water electrolysis technology. Therefore, the development of OER catalysts with low cost and high catalytic activity has extremely high significance.
Amorphous alloys have microstructure features of short range order and long range disorder, which places internal atoms in an unbalanced state, and can provide a large number of catalytically active sites. By introducing a certain amount of crystal phase into the amorphous matrix through a certain means, the amorphous composite material can be formed, which is not only an effective means for solving the problem of poor room temperature plasticity of the amorphous composite material, but also has been proved by researches that the amorphous-nanocrystalline heterostructure can effectively promote OER catalytic efficiency.
Disclosure of Invention
The invention aims to solve the problems that the existing OER catalyst contains noble metal, has high cost and has catalytic activity to be improved, and provides an amorphous composite material water electrolysis catalyst and a preparation method thereof.
The amorphous composite material water electrolysis catalyst of the invention comprises the following components in atomic ratio (38-42): (36-40): (1-5): (16-20) consists of iron, nickel, molybdenum and boron, wherein the microstructure is that nano crystals are uniformly distributed on an amorphous matrix, and the form of the amorphous composite material water electrolysis catalyst is surface porous metal microfilaments with the diameter of 35-50 mu m.
The preparation method of the amorphous composite material water electrolysis catalyst is realized according to the following steps:
1. according to atomic percent of Fe 38～42 Ni 36～40 Mo 1～5 B 16～20 Weighing iron, nickel, molybdenum and boron simple substances in a chemical formula as raw materials, and smelting the raw materials by using a vacuum arc smelting furnace to obtain a master alloy ingot;
2. carrying out suction casting on the master alloy ingot by adopting a water-cooling copper mold suction casting method to obtain an alloy rod;
3. placing the alloy rod into a crucible, vacuumizing a melt drawing device, filling argon protective atmosphere, preheating a copper wheel to 100-120 ℃ by using a baking lamp, starting the copper wheel to rotate, starting an induction coil power supply to heat and melt the alloy rod, adopting a melt drawing method to treat the alloy rod, controlling the rotating speed of the copper wheel to 1400-1700 r/min and the feeding speed to 30-50 mu m/s, and obtaining amorphous composite microfilaments;
4. immersing the amorphous composite microfilaments in corrosive liquid for dealloying treatment to obtain the amorphous composite electrolyzed water catalyst.
Preferably, the purity of the raw materials iron, nickel, molybdenum and boron simple substances is higher than 99.9%; the smelting process is carried out under the atmosphere of high-purity argon, and the pressure of the high-purity argon atmosphere is 35-50 KPa, and more preferably 50KPa; the working current of the smelting process is 250-500A, the turnover smelting times are at least 5 times, and the smelting time is at least 90s each time; the weight of the alloy ingot is about 50 g.
Preferably, the water-cooled copper die suction casting is performed under a high-purity argon atmosphere, and the pressure of the high-purity argon atmosphere is 35-50 KPa, and more preferably 50KPa; the diameter of the alloy rod obtained by suction casting is 8-15 mm, and the length is 50-70 mm.
Preferably, the microfilament preparation is carried out under vacuum, the vacuum degree being less than 8.0X10 -3 Pa; the preparation process is controlled by three parameters of the copper wheel rotating speed, the feeding speed and the induction coil heating current intensity, wherein the copper wheel rotating speed is 1400-1700 r/min, the feeding speed is 30-50 mu m/s, and the current intensity is 15-19A.
Preferably, the dealloying corrosive liquid adopts 0.1mol/LHF solution and 1mol/LHNO 3 Solution or 0.2mol/LH 3 PO 4 More preferably, a 0.1mol/L HF solution is used; the dealloying process is carried out for a treatment time of 30 to 60 minutes, more preferably for a treatment time of 60 minutes.
The invention also provides application of the amorphous composite material or the amorphous composite material microfilament prepared by the preparation method as an electrolytic water oxygen evolution catalyst.
The micron-sized amorphous composite material microfilament electrolysis water catalyst and the preparation method thereof provided by the invention have the following beneficial effects:
1. the amorphous alloy itself has a special atomic structure of short-range order and long-range disorder, atoms of the structure have higher Gibbs free energy, a large number of catalytic active sites can be provided for oxygen evolution reaction, and the amorphous-crystal heterostructure can further promote the activity, so that when the amorphous alloy has a proper number and size of nanocrystals to form an amorphous composite material, the oxygen evolution catalytic performance is also greatly improved.
2. High catalytic activity and current density of 10mA cm -2 The minimum overpotential is 233mV, which is lower than the noble metal analysis commonly used at presentOxygen catalyst IO 2 、RuO 2 Etc.
3. Can obtain extremely high current density which can reach 3A cm -2 The high current density required in the actual electrolyzed water industry can be easily achieved.
4. The micron-sized amorphous composite material microfilament electrolyzed water catalyst has the advantages of simple preparation method, low cost, high stability and excellent catalytic activity after being tested for 300 hours, and can be directly used as an electrode.
Drawings
FIG. 1 is a schematic diagram of a melt drawing apparatus for producing metal fibers in accordance with an embodiment of the present invention;
FIG. 2 is a photograph of an amorphous composite obtained in example 1;
FIG. 3 is a Scanning Electron Microscope (SEM) photograph of the amorphous composite material obtained in example 1;
FIG. 4 is an X-ray diffraction (XRD) pattern of the amorphous composite obtained in examples 1-3, wherein 1 represents example 1,2 represents example 2, and 3 represents example 3;
FIG. 5 is a Transmission Electron Microscope (TEM) photograph of the amorphous composite obtained in example 1, wherein (a) is a bright field image, (b) is a high resolution photograph (HR-TEM), and (c) is a selected area electron diffraction pattern (SAED);
FIG. 6 is a Transmission Electron Microscope (TEM) photograph of the amorphous composite obtained in example 2, wherein (a) is a bright field image, (b) is a high resolution photograph (HR-TEM), and (c) is a selected area electron diffraction pattern (SAED);
FIG. 7 is a Transmission Electron Microscope (TEM) photograph of the amorphous composite obtained in example 3, wherein (a) is a bright field image, (b) is a high resolution photograph (HR-TEM), and (c) is a selected area electron diffraction pattern (SAED);
FIG. 8 is an SEM photograph of the surface morphology of the surface porous amorphous composite material obtained after dealloying of example 1;
fig. 9 is a graph showing the catalytic polarization of oxygen evolution reaction of the amorphous composite materials obtained in examples 1 to 3, and examples 1,2 and 3 are shown in order along the arrow direction;
FIG. 10 is a Tafel slope (Tafel slope) graph of the oxygen evolution reaction of the amorphous composite obtained in examples 1-3, wherein 1 represents examples 1,2 represents examples 2, and 3 represents example 3;
FIG. 11 is a graph showing the ultra-large current catalytic activity test of the amorphous alloy composite material obtained in example 1;
FIG. 12 is a graph showing the stability test of the amorphous alloy composite material obtained in example 1 for 200 hours.
Detailed Description
The first embodiment is as follows: the amorphous composite material water electrolysis catalyst of the embodiment comprises the following components in atomic ratio (38-42): (36-40): (1-5): (16-20) consists of iron, nickel, molybdenum and boron, wherein the microstructure is that nano crystals are uniformly distributed on an amorphous matrix, and the form of the amorphous composite material water electrolysis catalyst is surface porous metal microfilaments with the diameter of 35-50 mu m.
The embodiment utilizes the amorphous composite microfilaments as the water electrolysis catalyst, and provides the micron-sized filiform FeNi-based amorphous composite water electrolysis OER catalyst and the preparation method thereof, and the catalyst has the advantages of high catalytic activity, strong stability, low cost, direct use as a reaction electrode and the like, can replace expensive noble metal catalysts, and can greatly reduce the cost of a water electrolysis device.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is that the amorphous composite material water electrolysis catalyst has an atomic number ratio of 40:38:4:18 are composed of iron, nickel, molybdenum and boron.
And a third specific embodiment: the preparation method of the amorphous composite material water electrolysis catalyst of the embodiment is implemented according to the following steps:
1. according to atomic percent of Fe 38～42 Ni 36～40 Mo 1～5 B 16～20 Weighing iron, nickel, molybdenum and boron simple substances in a chemical formula as raw materials, and smelting the raw materials by using a vacuum arc smelting furnace to obtain a master alloy ingot;
2. carrying out suction casting on the master alloy ingot by adopting a water-cooling copper mold suction casting method to obtain an alloy rod;
3. placing the alloy rod into a crucible, vacuumizing a melt drawing device, filling argon protective atmosphere, preheating a copper wheel to 100-160 ℃ by using a baking lamp, starting the copper wheel to rotate, starting an induction coil power supply to heat and melt the alloy rod, adopting a melt drawing method to treat the alloy rod, controlling the rotating speed of the copper wheel to 1400-1700 r/min and the feeding speed to 30-50 mu m/s, and obtaining amorphous composite microfilaments;
4. immersing the amorphous composite microfilaments in corrosive liquid for dealloying treatment to obtain the amorphous composite electrolyzed water catalyst.
In the process of preparing the alloy microfilaments by using the melt pulling method, the cooling speed is controlled by controlling the rotating speed of the copper wheel and preheating the copper wheel, namely, the melt cooling speed is controlled, so that the state (including the size, the number and the distribution of the nanocrystalline) of the nanocrystalline on the amorphous matrix is regulated and controlled. The copper wheel rotating speed and the cooling speed are in positive correlation, and the preheating temperature of the copper wheel influences the temperature difference between the copper wheel and the melt and is in negative correlation with the cooling speed. For the amorphous composite material provided by the invention, the cooling speed is most suitable when the copper wheel rotating speed is 1700r/min and the copper wheel is preheated to 150 ℃. The amorphous phase on the amorphous matrix of the amorphous composite material formed at the moment has the characteristics of large quantity, small size, uniform distribution and the like, which can certainly improve the interface area between the amorphous matrix and the crystalline phase, greatly increase the amorphous-crystalline heterostructure and obviously improve the oxygen evolution reaction catalytic performance of the amorphous composite material.
The specific embodiment IV is as follows: the third embodiment is different from the third embodiment in that in the first step, the working current of the arc melting furnace is controlled to be 300A-500A under the protection of argon atmosphere, the turnover melting times are at least 5 times, and the melting time of each time is 90 s-2 min.
Fifth embodiment: the difference between the embodiment and the third or fourth embodiment is that the water-cooled copper mold suction casting in the second step is performed under the atmosphere of high-purity argon (the purity is higher than 99.9%), the pressure of the high-purity argon atmosphere is 35-50 Kpa, and the cooling speed of the water-cooled copper mold suction casting is 200 ℃/s-300 ℃/s.
Specific embodiment six: the difference between the present embodiment and the third to fifth embodiments is that the alloy rod obtained in the second step has a diameter of 6 to 10mm and a length of 50 to 70mm.
Seventh embodiment: the difference between the present embodiment and the third to sixth embodiments is that the current intensity is controlled to 15 to 19A in the process of treating the alloy rod by the melt pulling method in the third step.
Eighth embodiment: the present embodiment is different from the seventh embodiment in that the copper wheel rotation speed is controlled to 1700r/min, the feed speed is controlled to 30 μm/s, and the current intensity is controlled to 17A.
Detailed description nine: the difference between the present embodiment and the fourth to eighth embodiments is that the etching solution in the fourth step is 0.1mol/LHF solution, 1mol/L HNO 3 Solution or 0.2mol/LH 3 PO 4 A solution.
Detailed description ten: the present embodiment differs from the ninth embodiment in that the dealloying time in the fourth step is 30 to 60 minutes.
Example 1: the preparation method of the surface porous amorphous composite material electrolytic water oxygen evolution catalyst is implemented according to the following steps:
1. firstly, the vacuum degree of a non-consumable arc melting furnace chamber is pumped to 7 multiplied by 10 -3 Under Pa, high-purity argon is filled into the furnace until the pressure of the cavity is 0.4MPa, and then residual oxygen element in the environment is absorbed by the smelting titanium block; under the protection of high-purity argon (99.999%), the atomic number ratio is 40:38:4:18, placing iron, nickel, molybdenum and boron simple substances into a non-consumable arc melting furnace, wherein the purity of raw materials is over 99.9 percent, the working current of the non-consumable arc melting furnace is 400A, and the non-consumable arc melting furnace is subjected to overturn melting for 5 times, and the melting time of each time is 2 minutes, so that button-shaped alloy ingots are obtained;
2. under the protection of argon atmosphere, a button-shaped alloy ingot is subjected to suction casting by a water-cooling copper die, and an alloy rod with the length of 60mm and the diameter of 10mm is obtained;
3. placing a master alloy rod into a boron nitride crucible, vacuumizing a melt drawing device, filling high-purity argon protective atmosphere, preheating a copper wheel to 150 ℃ by using a baking lamp, starting the copper wheel to rotate, starting an induction coil power supply to heat and melt the alloy rod, setting the rotating speed of the copper wheel to 1700r/min, controlling the feeding speed to be 30 mu m/s and the current intensity to be 17A, and preparing the alloy rod into alloy microfilaments of 35-40 mu m by using an extremely high cooling speed;
4. immersing the amorphous composite microfilaments in 0.1mol/L HF solution for dealloying for 30min, so that the amorphous composite microfilaments form a porous surface morphology, and elements on the surface of the microfilaments are transferred in a higher valence state, thereby improving the oxidability of elements such as iron, nickel and the like, further greatly improving the catalytic activity of the microfilaments, and obtaining the surface porous amorphous composite electrolytic water oxygen evolution catalyst.
The surface porous amorphous composite microfilaments with nanocrystalline are prepared in the embodiment. The microfilaments obtained by the embodiment have large specific surface area, expose more active sites, and benefit the unbalanced atomic structure of the amorphous composite material, so that the amorphous microfilaments have extremely high electrolytic water catalytic activity and stability, can be directly used as electrodes, and are very promising OER catalysts.
Example 2: the present embodiment is different from embodiment 1 in that the copper wheel rotation speed in the third step is set to 1400r/min.
The cooling speed of the embodiment is lower than that of the embodiment 1, and the number of the crystal phases distributed on the amorphous matrix in the prepared amorphous composite material is more, and the volume is larger.
Example 3: this example differs from examples 1 and 2 in that the copper wheel rotation speed in step three was set to 1100r/min.
The cooling rate of this example is lower than that of examples 1 and 2, the number of the nanocrystalline phases distributed on the large amorphous matrix inside the obtained amorphous composite is further increased, and the volume is further increased.
Table 1 shows the preparation parameters and current densities of 10mAcm for examples 1-3 -2 Time overpotential, tafel slope.
TABLE 1
Figure BDA0004139103690000061
Referring to fig. 1, fig. 1 is a schematic diagram illustrating a melt pulling method for preparing amorphous composite microfilaments according to an embodiment.
From fig. 1, it can be seen that the principle of the preparation of the metal microfilaments used in the present invention is as follows: putting a master alloy rod obtained by smelting and suction casting into a boron nitride crucible; heating and melting the alloy rod by an electromagnetic induction heating device, and obtaining an alloy pool with a protruding surface under the action of surface tension; the alloy puddle is slowly lifted up at a certain speed by using a feeding system, and after the puddle contacts with a copper wheel rotating at a high speed, a thin melt layer with a certain thickness is pulled out of the puddle, and is solidified and rounded into filaments at a very high cooling speed under the action of heat transfer and surface tension.
The preparation method of the embodiment mainly can be regulated and controlled by four parameters, namely the copper wheel rotating speed, the preheating temperature, the feeding speed and the induction heating current intensity. The embodiment mainly controls the cooling speed of the alloy melt by changing the rotation speed of the copper wheel and the preheating temperature, regulates and controls the structure and the energy state of the amorphous microfilaments, and further optimizes the electrolytic water catalysis performance of the microfilaments of the amorphous composite material.
Referring to fig. 2, a photograph of the amorphous composite material obtained in example 1 of fig. 2 is shown.
Referring to fig. 3, fig. 3 is a Scanning Electron Microscope (SEM) image of the amorphous composite material obtained in example 1.
From FIGS. 2 and 3, it can be seen that the amorphous composite material of the present invention is a microfilament having a length of 15 to 25cm and a diameter of about 40. Mu.m, and has a rounded shape and a smooth surface.
Referring to fig. 4, fig. 4 is a typical XRD diffractogram of the amorphous composite microfilaments obtained in example 1.
As can be seen from fig. 4, the XRD patterns of example 1 all show diffuse scattering peaks around 2θ=45°, and small and sharp crystalline peaks appear on the diffuse scattering peaks, which indicates that a certain number of crystalline phases appear on the amorphous matrix. In addition, it can be seen that the size of the crystalline peaks has the following rule: example 3> example 2> example 1, which shows that as the copper wheel speed decreases, the cooling rate also decreases, resulting in a gradual increase in the volume fraction of the crystalline phase in the amorphous composite. If the copper wheel is not preheated during the preparation of the microfilaments, the temperature difference between the copper wheel and the alloy melt can be obviously increased, the cooling speed is increased, the amorphous matrix cannot be nanocrystalline, the OER catalytic activity of the microfilaments can be obviously weakened, and the reaction rate and the energy conversion efficiency are greatly reduced.
Referring to fig. 5, fig. 5 is a Transmission Electron Microscope (TEM) photograph of the amorphous composite material obtained in example 1, wherein (a) is a bright field image, (b) is a high resolution photograph (HR-TEM), and (c) is a selected area electron diffraction pattern (SAED);
it is evident from the figure that the internal microstructure of the amorphous composite material obtained in example 1 is such that a certain number of uniformly distributed and small-sized nanocrystalline phases are present on the amorphous matrix.
Referring to fig. 6, fig. 6 is a Transmission Electron Microscope (TEM) photograph of the amorphous composite material obtained in example 2, wherein (a) is a bright field image, (b) is a high resolution photograph (HR-TEM), and (c) is a selected area electron diffraction pattern (SAED);
it can be seen in the figure that as the cooling rate decreases, the amorphous matrix of the amorphous composite of example 2 has a greater number of crystals distributed thereon and a greater size than that of example 1.
Referring to fig. 7, fig. 7 is a Transmission Electron Microscope (TEM) photograph of the amorphous composite material obtained in example 3, wherein (a) is a bright field image, (b) is a high resolution photograph (HR-TEM), and (c) is a selected area electron diffraction pattern (SAED);
it can be seen that as the copper wheel speed is further reduced and the cooling rate is further reduced, the crystal phase size is further increased.
Referring to fig. 8, fig. 8 is an SEM photograph of the surface morphology of the surface porous amorphous composite material obtained after dealloying in example 1.
From the graph, the surface of the amorphous composite microfilament after dealloying is shown as a porous morphology, so that the specific surface area of the amorphous microfilament is greatly increased, more active sites can be exposed, and the catalytic activity of the material is further improved.
Referring to fig. 9, fig. 9 is an OER catalytic polarization curve of the amorphous composites obtained in examples 1 to 3;
referring to fig. 10, fig. 10 is an OER Tafel slope (Tafel slope) curve of the amorphous composite materials obtained in examples 1 to 3;
from FIGS. 9, 10 and Table 1, it can be seen that the porous amorphous composites prepared in examples 1-3 all have very low overpotential and Tafel slope, especially in example 1 (i.e., when the copper wheel rotation speed during the preparation of the alloy microfilaments is 1700 r/min), and the current density is 10mAcm -2 The overpotential at this time was only 233mV, with Tafel slopes as low as 35mV dec -1 The performance of the catalyst is superior to that of the current commercial OER catalyst, which shows that the catalyst provided by the invention has extremely high catalytic activity.
Referring to fig. 11, fig. 11 is a graph showing the result of the ultra-large current OER catalytic activity test of the amorphous alloy composite material obtained in the example.
As can be seen from FIG. 11, the amorphous composite alloy microfilaments according to the present invention can achieve extremely high current density in OER reaction, and can exceed 3Acm -2 This far exceeds 500mAcm required for industrial applications -2 。
Referring to fig. 12, fig. 12 is a stability test curve of the amorphous alloy composite material obtained in example 1 for 200 hours.
It can be seen from fig. 12 that the overpotential does not change significantly in the continuous 200h constant current test, which indicates that the catalyst according to the present invention has high stability.

Claims (10)

1. The amorphous composite material water electrolysis catalyst is characterized in that the amorphous composite material water electrolysis catalyst comprises the following components in percentage by atomic number (38-42): (36-40): (1-5): (16-20) consists of iron, nickel, molybdenum and boron, wherein the microstructure is that nano crystals are uniformly distributed on an amorphous matrix, and the form of the amorphous composite material water electrolysis catalyst is surface porous metal microfilaments with the diameter of 35-50 mu m.
2. The amorphous composite material electrolyzed water catalyst according to claim 1, characterized in that the amorphous composite material electrolyzed water catalyst has a ratio of 40 by atomic number: 38:4:18 are composed of iron, nickel, molybdenum and boron.
3. The preparation method of the amorphous composite material electrolyzed water catalyst is characterized by comprising the following steps:
1. according to atomic percent of Fe 38～42 Ni 36～40 Mo 1～5 B 16～20 Weighing iron, nickel, molybdenum and boron simple substances in a chemical formula as raw materials, and smelting the raw materials by using a vacuum arc smelting furnace to obtain a master alloy ingot;
2. carrying out suction casting on the master alloy ingot by adopting a water-cooling copper mold suction casting method to obtain an alloy rod;
3. placing the alloy rod into a crucible, vacuumizing a melt drawing device, filling argon protective atmosphere, preheating a copper wheel to 100-160 ℃ by using a baking lamp, starting the copper wheel to rotate, starting an induction coil power supply to heat and melt the alloy rod, adopting a melt drawing method to treat the alloy rod, controlling the rotating speed of the copper wheel to 1400-1700 r/min and the feeding speed to 30-50 mu m/s, and obtaining amorphous composite microfilaments;
4. immersing the amorphous composite microfilaments in corrosive liquid for dealloying treatment to obtain the amorphous composite electrolyzed water catalyst.
4. The method for preparing the amorphous composite material electrolyzed water catalyst according to claim 3, wherein in the first step, the working current of an arc melting furnace is controlled to be 300A-500A under the protection of argon atmosphere, the turnover melting times are at least 5 times, and the melting time of each time is 90 s-2 min.
5. The method for preparing the amorphous composite material electrolyzed water catalyst according to claim 3, wherein the water-cooled copper mold suction casting in the second step is performed under a high-purity argon atmosphere, the pressure of the high-purity argon atmosphere is 35-50 Kpa, and the cooling speed of the water-cooled copper mold suction casting is 200 ℃/s-300 ℃/s.
6. The method for preparing an amorphous composite material electrolyzed water catalyst according to claim 3, wherein the diameter of the alloy rod obtained in the second step is 6-10 mm, and the length is 50-70 mm.
7. The method for preparing an amorphous composite material electrolyzed water catalyst according to claim 3, wherein the current intensity is controlled to be 15-19A in the process of treating the alloy rod by adopting a melt pulling method in the third step.
8. The method for preparing an amorphous composite material electrolyzed water catalyst according to claim 3, wherein the rotation speed of the copper wheel is controlled to 1700r/min, the feeding speed is controlled to 30 μm/s, and the current intensity is controlled to 17A.
9. The method for preparing an amorphous composite material electrolyzed water catalyst according to claim 3, wherein the corrosive liquid in the fourth step is 0.1mol/LHF solution, 1mol/LHNO 3 Solution or 0.2mol/LH 3 PO 4 A solution.
10. The method for preparing an amorphous composite material electrolyzed water catalyst according to claim 3, wherein the dealloying time in the fourth step is 30-60 min.
CN202310284133.5A 2023-03-22 2023-03-22 Amorphous composite material electrolyzed water catalyst and preparation method thereof Pending CN116334660A (en)

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CN117051429A (en) * 2023-08-29 2023-11-14 深圳大学 Platinum-based amorphous alloy electrolyzed water bifunctional catalyst and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117051429A (en) * 2023-08-29 2023-11-14 深圳大学 Platinum-based amorphous alloy electrolyzed water bifunctional catalyst and preparation method thereof
CN117051429B (en) * 2023-08-29 2024-04-19 深圳大学 Platinum-based amorphous alloy electrolyzed water bifunctional catalyst and preparation method thereof

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