CN110952110A - Nano-porous Pd-Fe-P-C material, preparation method thereof and application thereof in hydrogen production by water electrolysis - Google Patents

Nano-porous Pd-Fe-P-C material, preparation method thereof and application thereof in hydrogen production by water electrolysis Download PDF

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CN110952110A
CN110952110A CN201811133174.XA CN201811133174A CN110952110A CN 110952110 A CN110952110 A CN 110952110A CN 201811133174 A CN201811133174 A CN 201811133174A CN 110952110 A CN110952110 A CN 110952110A
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nano
porous
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alloy strip
alloy
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蒋睿
朱胜利
崔振铎
杨贤金
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Tianjin University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/003—Making ferrous alloys making amorphous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/02—Amorphous alloys with iron as the major constituent
    • 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
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C25F3/06—Etching of iron or steel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention provides a nano-porous Pd-Fe-P-C material, a preparation method thereof and application thereof in hydrogen production by electrolyzing water, wherein pure Fe and Fe are used3PFe3C and pure Pd are mixed according to a proportion and then are dissolved and smelted into an alloy ingot in an argon arc furnace, then a melt-out machine is used for melting and spraying the alloy ingot and rapidly cooling the alloy ingot into an alloy strip, the Pd-Fe-P-C alloy strip is subjected to electrochemical corrosion under constant potential, the Pd-Fe-P-C alloy strip is taken as a working electrode, the potential parameter is-0.3V-0.5V, the corrosion time is 800 plus 4000s, the electrolyte is 0.1-1M sulfuric acid aqueous solution, after the electrochemical corrosion is finished, a sample is taken out and then cleaned, and the sample is dried at the vacuum room temperature of 20-25 ℃ to obtain the nano porous Pd-Fe-P plus materialAnd C, material. The three-dimensional bicontinuous nano porous structure is prepared by a dealloying method, so that the stability of the material is improved, the specific surface area of the material is greatly increased, the material transmission is promoted, and the integral catalytic effect of the catalyst is finally improved.

Description

Nano-porous Pd-Fe-P-C material, preparation method thereof and application thereof in hydrogen production by water electrolysis
Technical Field
The invention relates to the technical field of novel nano-scale porous amorphous materials, in particular to a nano-scale porous Pd-Fe-P-C material, a preparation method thereof and application thereof in hydrogen production by water electrolysis.
Background
In recent years, with the massive combustion of fossil fuels, greenhouse gases are generated in large quantities, which causes an increasingly serious greenhouse effect, and with the increasingly exhausted reserves of fossil fuels on earth, new energy sources such as hydrogen are receiving wide attention from society. The ocean is the resource with the largest reserve on the earth and inexhaustible, so that the hydrogen production by water electrolysis becomes one of the current scientific research hotspots.
Although noble metal catalysts such as pure Pd and Pt have good intrinsic catalytic activity, the catalytic activity sites are small, so that the overall catalytic activity is not high, the stability is limited by the loading mode, and most of the catalysts are in a carbon-supported form, so that nanoparticles are easy to fall off, and the stability is poor.
The nanoporous material prepared by the electrochemical dealloying method is a catalyst that does not require a support. The common carbon-supported nanoparticle catalyst can generate a serious coarsening phenomenon in the long-range catalysis process, so that the contact area between the nanoparticles and the carbon material is reduced.
An amorphous structure can be generated through electrochemical dealloying, the amorphous structure is short-range ordered long-range disorder, the entropy value is high, the disorder degree is high, so that the defects of interatomic coordination of the amorphous structure occur, and the defects are favorable for improving the catalytic activity. Therefore, the use of nano-porous amorphous materials to replace carbon-supported noble metal catalysts is a promising research direction.
Disclosure of Invention
The invention overcomes the defects in the prior art, provides a nano-porous Pd-Fe-P-C material, a preparation method thereof and application thereof in hydrogen production by electrolyzing water, and prepares a three-dimensional bicontinuous nano-porous structure by a dealloying method, thereby not only increasing the stability of the material, but also greatly increasing the specific surface area of the material and promoting the material transmission, and finally improving the integral catalytic effect of the catalyst.
The purpose of the invention is realized by the following technical scheme.
A nano-porous Pd-Fe-P-C material and a preparation method thereof are carried out according to the following steps:
step 1, preparing Pd-Fe-P-C alloy strip
Mixing pure Fe and Fe3PFe3C and pure Pd are proportioned in proportion and then are melted in an argon arc furnace to form an alloy ingot, then the alloy ingot is melted by using a melt spinning machine and is sprayed out to be rapidly cooled to form an alloy strip, wherein the mass percent of pure Fe is 8-16%, and Fe332 to 45 percent of P and Fe3The mass percent of C is 28-36%, the mass percent of pure Pd is 12-25%, and the sum of the four components is 100%.
In the step 1, the prepared Pd-Fe-P-C (amorphous) alloy strip is cut into small sections, the cut strip is put into a beaker and is ultrasonically cleaned in absolute ethyl alcohol, and then the strip is vacuum-dried in a vacuum drying oven at the room temperature of 20-25 ℃.
In step 1, the mass percent of pure Fe is 10% -15%, and Fe335 to 40 percent of P and Fe330-35% of C and 15-20% of pure Pd.
In step 1, the raw materials are pure Fe and Fe3P、Fe3C and pure Pd, mixing the raw materials according to a certain proportion, putting the mixture into an argon arc melting furnace, starting to melt for 4-5 times to enable the alloy components to be mixed more uniformly, taking out an alloy ingot and crushing the alloy ingot, taking the fragments, ultrasonically cleaning the fragments by absolute ethyl alcohol, putting the fragments into a clean quartz tube, placing the quartz tube into a ribbon throwing machine, pumping high vacuum, spraying the melted liquid alloy onto a copper roller rotating at high speed, and quickly cooling the liquid to form an amorphous ribbon instantly.
In step 1, the melt spinning machine needs to be pumped to 1 × 10-3Pa-1×10-2Pa, the rotating speed of the copper roller needs to be controlled at 3000-4000 rpm, and the pressure difference between the quartz tube and the interior of the furnace body needs to be controlled at 0.1-0.5 Pa.
In step 1, the prepared Pd-Fe-P-C alloy strip has the atomic content (mole percent) of Fe of 75-85%, the content of P of 5-15%, the content of C of 5-15% and the content of Pd of 5-15%, the four atomic ratios are added to be one hundred percent, and has an iron crystal structure, and the element P, C and Pd exist in a sample in the form of solid solution defects.
Step 2, preparing the nano-porous Pd-Fe-P-C material by adopting an electrochemical dealloying method
And (2) carrying out electrochemical corrosion on the Pd-Fe-P-C alloy strip prepared in the step (1) under constant potential, taking the Pd-Fe-P-C alloy strip as a working electrode, carrying out electrochemical corrosion on the Pd-Fe-P-C alloy strip with the potential parameter of-0.3V-0.5V, the corrosion time of 800-4000s and the electrolyte of 0.1-1M sulfuric acid aqueous solution, taking out a sample, cleaning, and drying at the vacuum room temperature of 20-25 ℃ to obtain the nano porous Pd-Fe-P-C material.
In the step 2, a calomel electrode is used as a reference electrode, a platinum net is used as a counter electrode, and a Pd-Fe-P-C alloy strip is used as a working electrode to carry out constant potential electrochemical corrosion.
In step 2, the corrosion potential is set to be-0.1V-0.2V, the time is set to be 1000-3600s, and the electrolyte is 0.5-1M sulfuric acid aqueous solution.
In the step 2, the sample is taken out and washed with deionized water and absolute ethyl alcohol for five times respectively, and then dried at the room temperature of 20-25 ℃ in vacuum to prevent oxidation, and finally the nano-porous Pd-Fe-P-C material is obtained.
The application of the nano-porous Pd-Fe-P-C material in the water electrolysis cathode catalytic hydrogen production (namely the application in the water electrolysis hydrogen production) has the current density of 10mA/cm2When the material is used, the overpotential of the nano-porous Pd-Fe-P-C material is 25-30 mV.
The invention has the beneficial effects that: compared with the prior art, the common carbon-supported nanoparticle catalyst can generate serious coarsening phenomenon in the catalysis process, so that the contact area of the nanoparticles and the carbon material is reduced, the nanoparticles are easy to fall off and dissolve in the catalysis reaction process, the stability is poor, the three-dimensional bicontinuous nano porous structure is prepared by a dealloying method, the material stability is increased, the specific surface area of the material is greatly increased, the material transmission is promoted, the integral catalysis effect of the catalyst is finally improved, the number of active sites of the material is increased by introducing nonmetallic elements such as C, P and the like, the intrinsic catalytic activity of the material is improved, the performance of the material in water electrolysis is improved by doping P, C, the dosage of the conventional noble metal catalyst Pd is reduced, and the cost is reduced; the nano-porous Pd-Fe-P-C material obtained by the method is an amorphous material, and the amorphous material is characterized in that the defects of interatomic coordination of the nano-porous Pd-Fe-P-C material are caused by short-range order, long-range disorder, high entropy and high chaos, and the defects are favorable for improving the catalytic activity.
Drawings
FIG. 1 is an SEM image of a nanoporous Pd-Fe-P-C material prepared in example 1;
FIG. 2 is a TEM image of the nanoporous Pd-Fe-P-C material prepared in example 1;
FIG. 3 is an XRD pattern of the nanoporous Pd-Fe-P-C material prepared in example 1;
FIG. 4 is a LSV curve diagram of the nano-porous Pd-Fe-P-C material prepared in example 1 when used as a cathode material for hydrogen evolution by water electrolysis;
FIG. 5 is the LSV curve diagram of the nano-porous Pd-Fe-P-C material prepared in example 2 when used as cathode material for hydrogen evolution by water electrolysis.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
1. Weighing 0.82g of pure iron (Fe) and iron phosphide (Fe)3P)2.93g, iron carbide (Fe)3C)2.65 g. 1.6g of pure palladium (Pd) was sampled for a total of 8 g.
2. And (3) putting 8g of sample into an argon protection arc melting furnace, pumping high vacuum by using a molecular pump, introducing high-purity argon protection atmosphere, and melting for 5 times to ensure that the internal components of the alloy are uniform. To obtain Fe70Pd10P10C10And (3) alloy ingots.
3. Then taking out the alloy ingot to be crushed, taking the fragments, ultrasonically cleaning the fragments by alcohol, placing the fragments in a ribbon throwing machine, pumping high vacuum, then cleaning and heating the alloy ingot to be molten, spraying liquid alloy on a copper roller rotating at high speed, and quickly cooling the liquid to form an amorphous ribbon instantly. The melt-spun machine needs to be drawn to 7 multiplied by 10-3Pa. The rotation speed of the copper roller needs to be controlled at 3500 rpm. The pressure difference between the quartz tube and the interior of the furnace body needs to be controlled at 0.4 Pa. To obtain Fe70Pd10P10C10Alloy strip.
4. Mixing Fe70Pd10P10C10The alloy strip was cut off, the strip having a width of about 5mm and a length of about 15 mm. Putting the cut strips into a beaker, performing ultrasonic treatment in absolute ethyl alcohol for 30min, and finally performing vacuum drying at room temperature.
5. Preparing an electrochemical workstation and a three-electrode system, taking a calomel electrode as a reference electrode, a platinum net as a counter electrode, an alloy strip as a working electrode, and mixing Fe70Pd10P10C10The strip is subjected to electrochemical corrosion at constant potential, the electrolyte is diluted with 0.5M of H2SO4An aqueous solution. Therefore, the electric potential parameter is set to-0.05V, the etching time is 3600s, and the etching is carried out until the current density is less than 100 muA, and the etching reaction is considered to be finished. Separating out the sample by using a dropper, washing the sample by using deionized water for 5 times, washing the sample by using absolute ethyl alcohol for 5 times, and then continuously performing vacuum drying for 12 hours at room temperature by using a vacuum drying oven to finally obtain the nano porous Pd-Fe-P-C material.
As shown in FIG. 1, SEM photograph of sample with magnification of 10k, 100k and 180k shows that the nano-porous Pd-Fe-P-C material is three-dimensional bicontinuous spongy nano-porous structure with large specific surface area and thus exposing more active sites, and the pore size and ligament size of the nano-porous Pd-Fe-P-C material are 8-12 nm.
As shown in FIG. 2, the pores, pore diameters and ligament sizes of the nanoporous Pd-Fe-P-C material are 8-12nm, which are uniformly distributed, can be clearly seen through a transmission electron microscope, and meanwhile, the nanoporous Pd-Fe-P-C material is found to have no crystal part, and a diffraction ring proves that the nanoporous Pd-Fe-P-C material is a uniform amorphous structure.
As shown in FIG. 3, the nano-porous Pd-Fe-P-C material is characterized by XRD and has only an envelope peak without a characteristic peak, and the internal structure of the nano-porous Pd-Fe-P-C material is an amorphous structure.
By using a three-electrode system, a calomel electrode as a reference electrode, a platinum net as a counter electrode, the nano-porous Pd-Fe-P-C material as a working electrode (as a cathode) and 0.5M dilute sulfuric acid aqueous solution as electrolyte, as shown in figure 4, according to an LSV curve, the nano-porous Pd-Fe-P-C material has a current density of 10mA/cm2The overpotential is 30mV, the performance is close to the sameThe platinum-carbon electrode has excellent cathode catalytic hydrogen production performance in the current commercial platinum-carbon electrode. The overpotential of the current commercial platinum-carbon electrode is 30mV (manufacturer Alfa Aesar).
Example 2
1. Weighing 0.82g of pure iron (Fe) and iron phosphide (Fe)3P)2.93g, iron carbide (Fe)3C)2.65 g. 1.6g of pure palladium (Pd) was sampled for a total of 8 g.
2. And (3) putting 8g of sample into an argon protection arc melting furnace, pumping high vacuum by using a molecular pump, introducing high-purity argon protection atmosphere, and melting for 5 times to ensure that the internal components of the alloy are uniform. To obtain Fe70Pd10P10C10And (3) alloy ingots.
3. Then taking out the alloy ingot to be crushed, taking the fragments, ultrasonically cleaning the fragments by alcohol, placing the fragments in a ribbon throwing machine, pumping high vacuum, then cleaning and heating the alloy ingot to be molten, spraying liquid alloy on a copper roller rotating at high speed, and quickly cooling the liquid to form an amorphous ribbon instantly. The melt-spun machine needs to be drawn to 7 multiplied by 10-3Pa. The rotation speed of the copper roller needs to be controlled at 3500 rpm. The pressure difference between the quartz tube and the interior of the furnace body needs to be controlled at 0.4 Pa. To obtain Fe70Pd10P10C10Alloy strip.
4. Mixing Fe70Pd10P10C10The alloy strip was cut off, the strip having a width of about 5mm and a length of about 15 mm. Putting the cut strips into a beaker, performing ultrasonic treatment in absolute ethyl alcohol for 30min, and finally performing vacuum drying at room temperature.
5. Preparing an electrochemical workstation and a three-electrode system, taking a calomel electrode as a reference electrode, a platinum net as a counter electrode, an alloy strip as a working electrode, and mixing Fe70Pd10P10C10The strip is subjected to electrochemical corrosion at constant potential, the electrolyte is diluted with 0.5M of H2SO4An aqueous solution. Therefore, the potential parameter is set to-0.01V, the etching time is 3600s, and the etching is carried out until the current density is less than 100 muA, and the etching reaction is considered to be finished. Separating out the sample by using a dropper, washing the sample by using deionized water for 5 times, washing the sample by using absolute ethyl alcohol for 5 times, and then continuously performing vacuum drying for 12 hours at room temperature by using a vacuum drying oven to finally obtain the nano porous Pd-Fe-P-C material.
By using a three-electrode system, a calomel electrode as a reference electrode, a platinum net as a counter electrode, the nano-porous Pd-Fe-P-C material of the invention as a working electrode (as a cathode), and an electrolyte of 0.5M dilute sulfuric acid aqueous solution, as shown in figure 5, according to an LSV curve, the nano-porous Pd-Fe-P-C material has a current density of 10mA/cm2The overpotential is 25mV, the performance is higher than that of the current commercial platinum-carbon electrode, and the hydrogen production performance by cathode catalysis is excellent. The overpotential of the current commercial platinum-carbon electrode is 30mV (manufacturer Alfa Aesar).
Example 3
Weighing pure iron, iron phosphide, iron carbide and pure palladium for smelting to obtain Fe75Pd5P10C10And (3) alloy ingots. Then taking out the alloy ingot to be crushed, taking the fragments, ultrasonically cleaning the fragments by absolute ethyl alcohol, placing the fragments into a clean quartz tube, placing the fragments into a ribbon throwing machine, pumping high vacuum, and then spraying the melted liquid alloy onto a copper roller rotating at high speed to ensure that the liquid is rapidly cooled to form an amorphous ribbon instantly. The melt-spun machine needs to be drawn to 1 multiplied by 10-3Pa. The rotation speed of the copper roller needs to be controlled at 4000 revolutions per minute. The pressure difference between the quartz tube and the interior of the furnace body needs to be controlled at 0.5 Pa. To obtain Fe75Pd5P10C10A strip of crystalline alloy. Cutting into small segments, wherein the width of the strip is 8mm, and the length of the strip is 20 mm. The cut strips were put into a beaker, sonicated in absolute ethanol for 20min, then washed with absolute ethanol, and then placed in a vacuum drying oven at room temperature for 12 hours.
Preparing an electrochemical workstation and a three-electrode system, taking a calomel electrode as a reference electrode, taking a platinum net as a counter electrode, taking an alloy strip as a working electrode, carrying out electrochemical corrosion on a Pd-Fe-P-C strip under constant potential, using 0.6M dilute sulfuric acid aqueous solution as electrolyte, sequentially washing the electrolyte with deionized water and absolute ethyl alcohol after taking out a sample, and then drying the sample at room temperature in vacuum to finally obtain the nano porous Pd-Fe-P-C material.
Example 4
Weighing pure iron, iron phosphide, iron carbide and pure palladium for smelting to obtain Fe55Pd5P5C5And (3) alloy ingots. Then taking out the alloy ingot to be crushed, taking the fragments, ultrasonically cleaning the fragments by absolute ethyl alcohol, placing the fragments into a clean quartz tube, placing the fragments into a ribbon throwing machine, pumping high vacuum, and then spraying the melted liquid alloy onto a copper roller rotating at high speed to ensure that the liquid is rapidly cooled to form an amorphous ribbon instantly. The melt-spun machine needs to be drawn to 5 multiplied by 10-3Pa. The rotation speed of the copper roller needs to be controlled at 3600 revolutions per minute. The pressure difference between the quartz tube and the interior of the furnace body needs to be controlled at 0.1 Pa. To obtain Fe55Pd5P5C5A strip of crystalline alloy. Cutting into small segments, wherein the width of the strip is 8mm, and the length of the strip is 20 mm. The cut strips were put into a beaker, sonicated in absolute ethanol for 20min, then washed with absolute ethanol, and then placed in a vacuum drying oven at room temperature for 12 hours.
Preparing an electrochemical workstation and a three-electrode system, taking a calomel electrode as a reference electrode, taking a platinum net as a counter electrode, taking an alloy strip as a working electrode, carrying out electrochemical corrosion on a Pd-Fe-P-C strip under constant potential, using 0.8M dilute sulfuric acid aqueous solution as electrolyte, sequentially washing the electrolyte with deionized water and absolute ethyl alcohol after taking out a sample, and then drying the sample at room temperature in vacuum to finally obtain the nano porous Pd-Fe-P-C material.
Example 5
Weighing pure iron, iron phosphide, iron carbide and pure palladium for smelting to obtain Fe75Pd5P10C10And (3) alloy ingots. Then taking out the alloy ingot to be crushed, taking the fragments, ultrasonically cleaning the fragments by absolute ethyl alcohol, placing the fragments into a clean quartz tube, placing the fragments into a ribbon throwing machine, pumping high vacuum, and then spraying the melted liquid alloy onto a copper roller rotating at high speed to ensure that the liquid is rapidly cooled to form an amorphous ribbon instantly. The melt-spun machine needs to be drawn to 8 multiplied by 10-3Pa. The rotation speed of the copper roller needs to be controlled at 3800 rpm. The pressure difference between the quartz tube and the interior of the furnace body needs to be controlled at 0.4 Pa. To obtain Fe75Pd5P10C10A strip of crystalline alloy. Cutting into small segments, wherein the width of the strip is 8mm, and the length of the strip is 20 mm. Putting the cut strips into a beaker, performing ultrasonic treatment in absolute ethyl alcohol for 20min, then cleaning with absolute ethyl alcohol, and then placing in a vacuum drying oven at room temperature for 12 hours。
Preparing an electrochemical workstation and a three-electrode system, taking a calomel electrode as a reference electrode, taking a platinum net as a counter electrode, taking an alloy strip as a working electrode, carrying out electrochemical corrosion on a Pd-Fe-P-C strip under constant potential, using 1M dilute sulfuric acid aqueous solution as electrolyte, sequentially washing the electrolyte with deionized water and absolute ethyl alcohol after taking out a sample, and then drying the sample at room temperature in vacuum to finally obtain the nano porous Pd-Fe-P-C material, wherein the potential parameter is-0.1V, and the corrosion time is 3600 s.
Example 6
Weighing pure iron, iron phosphide, iron carbide and pure palladium for smelting to obtain Fe75Pd5P10C10And (3) alloy ingots. Then taking out the alloy ingot to be crushed, taking the fragments, ultrasonically cleaning the fragments by absolute ethyl alcohol, placing the fragments into a clean quartz tube, placing the fragments into a ribbon throwing machine, pumping high vacuum, and then spraying the melted liquid alloy onto a copper roller rotating at high speed to ensure that the liquid is rapidly cooled to form an amorphous ribbon instantly. The melt-spun machine needs to be drawn to 9 multiplied by 10-3Pa. The rotation speed of the copper roller needs to be controlled at 3200 rpm. The pressure difference between the quartz tube and the interior of the furnace body needs to be controlled at 0.3 Pa. To obtain Fe75Pd5P10C10A strip of crystalline alloy. Cutting into small segments, wherein the width of the strip is 8mm, and the length of the strip is 20 mm. The cut strips were put into a beaker, sonicated in absolute ethanol for 20min, then washed with absolute ethanol, and then placed in a vacuum drying oven at room temperature for 12 hours.
Preparing an electrochemical workstation and a three-electrode system, taking a calomel electrode as a reference electrode, taking a platinum net as a counter electrode, taking an alloy strip as a working electrode, carrying out electrochemical corrosion on a Pd-Fe-P-C strip under constant potential, using 0.5M dilute sulfuric acid aqueous solution as electrolyte, sequentially washing the electrolyte with deionized water and absolute ethyl alcohol after taking out a sample, and then drying the sample at room temperature in vacuum to finally obtain the nano porous Pd-Fe-P-C material.
The adjustment of the process parameters according to the content of the invention can realize the preparation of the nano material and show the performance basically consistent with the embodiment of the invention, and the nano crystal material with the nano porous structure has three-dimensional bicontinuous spongy nano porous materialThe structure, the pore diameter and the ligament size are 8-12nm, the nano porous Pd-Fe-P-C material forms a short-range ordered long-range disordered amorphous structure, and the current density is 10mA/cm2The overpotential in the case of time is 25-30 mV.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (10)

1. A nano-porous Pd-Fe-P-C material is characterized in that: the method comprises the following steps:
step 1, preparing Pd-Fe-P-C alloy strip
Mixing pure Fe and Fe3PFe3C and pure Pd are proportioned in proportion and then are melted in an argon arc furnace to form an alloy ingot, then the alloy ingot is melted by using a melt spinning machine and is sprayed out to be rapidly cooled to form an alloy strip, wherein the mass percent of pure Fe is 8-16%, and Fe332 to 45 percent of P and Fe3The mass percent of C is 28-36%, the mass percent of pure Pd is 12-25%, and the sum of the four components is 100%;
step 2, preparing the nano-porous Pd-Fe-P-C material by adopting an electrochemical dealloying method
And (2) carrying out electrochemical corrosion on the Pd-Fe-P-C alloy strip prepared in the step (1) under constant potential, taking the Pd-Fe-P-C alloy strip as a working electrode, carrying out electrochemical corrosion on the Pd-Fe-P-C alloy strip with the potential parameter of-0.3V-0.5V, the corrosion time of 800-4000s and the electrolyte of 0.1-1M sulfuric acid aqueous solution, taking out a sample, cleaning, and drying at the vacuum room temperature of 20-25 ℃ to obtain the nano porous Pd-Fe-P-C material.
2. The nanoporous Pd-Fe-P-C material according to claim 1, wherein: in step 1, the mass percent of pure Fe is 10% -15%, and Fe335 to 40 percent of P and Fe330-35% of C and 15-20% of pure Pd.
3. The nanoporous Pd-Fe-P-C material according to claim 1, wherein: in step 1, the melt spinning machine needs to be pumped to 1 × 10-3Pa-1×10-2Pa, the rotating speed of the copper roller needs to be controlled at 3000-4000 rpm, and the pressure difference between the quartz tube and the interior of the furnace body needs to be controlled at 0.1-0.5 Pa.
4. The nanoporous Pd-Fe-P-C material according to claim 1, wherein: in the step 2, a calomel electrode is used as a reference electrode, a platinum net is used as a counter electrode, a Pd-Fe-P-C alloy strip is used as a working electrode to carry out constant potential electrochemical corrosion, the corrosion potential is set to be minus 0.1V to 0.2V, the time is set to be 1000-3600s, and the electrolyte is 0.5-1M sulfuric acid aqueous solution.
5. Method for preparing a nanoporous Pd-Fe-P-C material according to any one of claims 1-4, characterized in that: the method comprises the following steps:
step 1, preparing Pd-Fe-P-C alloy strip
Mixing pure Fe and Fe3PFe3C and pure Pd are proportioned in proportion and then are melted in an argon arc furnace to form an alloy ingot, then the alloy ingot is melted by using a melt spinning machine and is sprayed out to be rapidly cooled to form an alloy strip, wherein the mass percent of pure Fe is 8-16%, and Fe332 to 45 percent of P and Fe3The mass percent of C is 28-36%, the mass percent of pure Pd is 12-25%, and the sum of the four components is 100%;
step 2, preparing the nano-porous Pd-Fe-P-C material by adopting an electrochemical dealloying method
And (2) carrying out electrochemical corrosion on the Pd-Fe-P-C alloy strip prepared in the step (1) under constant potential, taking the Pd-Fe-P-C alloy strip as a working electrode, carrying out electrochemical corrosion on the Pd-Fe-P-C alloy strip with the potential parameter of-0.3V-0.5V, the corrosion time of 800-4000s and the electrolyte of 0.1-1M sulfuric acid aqueous solution, taking out a sample, cleaning, and drying at the vacuum room temperature of 20-25 ℃ to obtain the nano porous Pd-Fe-P-C material.
6. The method for preparing the nano-porous Pd-Fe-P-C material as claimed in claim 5Characterized in that: in step 1, the mass percent of pure Fe is 10% -15%, and Fe335 to 40 percent of P and Fe330-35% of C and 15-20% of pure Pd.
7. The method for preparing the nano-porous Pd-Fe-P-C material as claimed in claim 5, wherein: in step 1, the melt spinning machine needs to be pumped to 1 × 10-3Pa-1×10-2Pa, the rotating speed of the copper roller needs to be controlled at 3000-4000 rpm, and the pressure difference between the quartz tube and the interior of the furnace body needs to be controlled at 0.1-0.5 Pa.
8. The method for preparing the nano-porous Pd-Fe-P-C material as claimed in claim 5, wherein: in the step 2, a calomel electrode is used as a reference electrode, a platinum net is used as a counter electrode, and a Pd-Fe-P-C alloy strip is used as a working electrode to carry out constant potential electrochemical corrosion.
9. The method for preparing the nano-porous Pd-Fe-P-C material as claimed in claim 5, wherein: setting the corrosion potential at-0.1V-0.2V, the time at 1000-3600s, and the electrolyte at 0.5-1M sulfuric acid aqueous solution.
10. The application of the nano-porous Pd-Fe-P-C material as claimed in any one of claims 1 to 4 in hydrogen production by water electrolysis, wherein: at a current density of 10mA/cm2When the material is used, the overpotential of the nano-porous Pd-Fe-P-C material is 25-30 mV.
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