CN115799546A - Cobalt-doped platinum iron nickel copper alloy hydrogen evolution catalyst, preparation method and hydrogen fuel cell - Google Patents
Cobalt-doped platinum iron nickel copper alloy hydrogen evolution catalyst, preparation method and hydrogen fuel cell Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000001257 hydrogen Substances 0.000 title claims abstract description 99
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 99
- KDZYLMLLBUKPFG-UHFFFAOYSA-N [Cu].[Ni].[Fe].[Pt] Chemical compound [Cu].[Ni].[Fe].[Pt] KDZYLMLLBUKPFG-UHFFFAOYSA-N 0.000 title claims abstract description 88
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- ZWGTVKDEOPDFGW-UHFFFAOYSA-N hexadecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[NH3+] ZWGTVKDEOPDFGW-UHFFFAOYSA-N 0.000 claims description 21
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- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims description 5
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 4
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- 239000000243 solution Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
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- 229910001868 water Inorganic materials 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- IUNUQZUNCWXDMP-UHFFFAOYSA-N copper iron platinum Chemical compound [Fe][Pt][Cu] IUNUQZUNCWXDMP-UHFFFAOYSA-N 0.000 description 2
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- 239000003245 coal Substances 0.000 description 1
- GOECOOJIPSGIIV-UHFFFAOYSA-N copper iron nickel Chemical compound [Fe].[Ni].[Cu] GOECOOJIPSGIIV-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- 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
- Y02E60/50—Fuel cells
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Abstract
The application belongs to the technical field of catalysts, and particularly relates to a cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst, a preparation method and a hydrogen fuel cell; the cobalt-doped platinum iron nickel copper alloy hydrogen evolution catalyst comprises a carrier and a cobalt-doped platinum iron nickel copper solid solution alloy loaded on the carrier, wherein the compression effect caused by the small amount of doping of cobalt causes the center of a d band of a platinum-based solid solution alloy platinum iron nickel copper catalytic material to move downwards, so that the platinum-iron nickel copper catalytic material deviates from a Fermi level, the interaction between the catalyst and a surface adsorbent is weakened, the material transfer and hydrogen evolution reaction kinetics are promoted, the catalytic performance of the platinum-iron nickel copper catalytic material is obviously improved, and the technical problems of weaker hydrogen evolution reaction kinetics and lower hydrogen evolution catalytic performance of the platinum-based multi-element solid solution alloy in the prior art are solved.
Description
Technical Field
The application belongs to the technical field of catalysts, and particularly relates to a cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst, a preparation method thereof and a hydrogen fuel cell.
Background
Energy crisis and environmental crisis caused by long-term use of fossil fuels are more and more emphasized, development and storage of green new energy become urgent needs, and hydrogen is generally considered as an ideal energy carrier due to high energy density and environmental friendliness.
Carbon dioxide emission is generated in coal gasification and partial oxidation hydrogen production in the conventional industry, so that the greenhouse effect is enhanced, carbon dioxide is not generated in electrolyzed water, and oxygen and hydrogen are generated, so that the electrolyzed water is an effective and environment-friendly way for generating hydrogen at present; platinum and platinum-based catalysts have lower reaction energy barrier and excellent catalytic performance, are commonly used electrolytic water hydrogen evolution catalysts, but platinum has low resource reserves and high cost, so that the production cost of the catalyst can be reduced and the shortage of platinum element reserves can be relieved by combining non-noble metals such as iron, cobalt, nickel, copper, molybdenum and tungsten with platinum noble metals to form the multi-element solid solution alloy. However, the hydrogen evolution reaction kinetics of the existing platinum-based multi-element solid solution alloy is weaker, and the hydrogen evolution catalytic performance needs to be improved.
Disclosure of Invention
In view of the above, the application provides a cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst, a preparation method thereof and a hydrogen fuel cell, and aims to solve the technical problems that a platinum-based multi-element solid solution alloy in the prior art is weak in hydrogen evolution reaction kinetics and low in hydrogen evolution catalytic performance.
The first aspect of the application provides a cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst, which comprises a carrier and cobalt-doped platinum-iron-nickel-copper solid solution alloy particles;
the carrier supports the cobalt-doped platinum-iron-nickel-copper solid solution alloy particles.
Preferably, the cobalt-doped platinum-iron-nickel-copper solid solution alloy particles are cubic particles.
Preferably, the particle size of the cobalt-doped platinum-iron-nickel-copper solid solution alloy particles is 5-15 nm.
Preferably, the support is a carbon nanotube.
Preferably, the cobalt-doped platinum-iron-nickel-copper solid solution alloy particles have an atomic ratio of platinum, iron, cobalt, nickel and copper of 56.04:6.31:0.42:14.17:23.06.
the second aspect of the application provides a preparation method of a cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst, which comprises the following steps: adding a mixed solution containing hexadecyl ammonium chloride and oleylamine into a dispersion liquid containing a metal organic compound, glucose, molybdenum hexacarbonyl and a carrier, and carrying out normal-pressure heating reaction to obtain a cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst;
the metal organic compound comprises platinum acetylacetonate, iron acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate and copper acetylacetonate.
Preferably, the temperature of the normal pressure heating reaction is 150-250 ℃ and the time is 1-4 hours.
Preferably, the preparation method of the mixed solution containing the hexadecyl ammonium chloride and the oleylamine comprises the steps of dissolving the hexadecyl ammonium chloride in the oleylamine, and then carrying out ultrasonic treatment to obtain the mixed solution containing the hexadecyl ammonium chloride and the oleylamine.
Preferably, the preparation method of the dispersion liquid containing the metal organic compound, glucose, molybdenum hexacarbonyl and the carrier comprises mixing the metal organic compound, glucose, molybdenum hexacarbonyl and the carrier, and then carrying out ultrasonic treatment to obtain the dispersion liquid containing the metal organic compound, glucose, molybdenum hexacarbonyl and the carrier.
Preferably, after the cobalt-doped platinum iron nickel copper alloy hydrogen evolution catalyst is obtained, the method further comprises post-treatment, wherein the post-treatment comprises the step of soaking the cobalt-doped platinum iron nickel copper alloy hydrogen evolution catalyst in an acetic acid alcohol solution to remove residual oleylamine.
Preferably, the mass ratio of the hexadecyl ammonium chloride, the molybdenum hexacarbonyl, the oleylamine, the platinum acetylacetonate, the iron acetylacetonate, the cobalt acetylacetonate, the nickel acetylacetonate, and the copper acetylacetonate is 100:30:16.2:15:3.37:3.4:2.45:2.5.
a third aspect of the present application provides a hydrogen fuel cell comprising a bipolar plate and membrane electrodes on both sides thereof;
the membrane electrode comprises a proton exchange membrane, a catalyst layer and a diffusion layer which are sequentially superposed;
the catalyst layer comprises the cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst.
In summary, the present application provides a cobalt-doped platinum iron nickel copper alloy hydrogen evolution catalyst, a preparation method thereof, and a hydrogen fuel cell, wherein the cobalt-doped platinum iron nickel copper alloy hydrogen evolution catalyst comprises a carrier and a cobalt-doped platinum iron nickel copper solid solution alloy loaded thereon, and compared with a platinum-based solid solution alloy platinum iron nickel copper catalytic material, a compression effect caused by a small amount of doping (0.42%) of cobalt causes a d-band center of the platinum-based solid solution alloy platinum iron nickel copper catalytic material to move down, so that the platinum iron nickel copper catalytic material deviates from a fermi level, an interaction between the catalyst and a surface adsorbent is weakened, a mass transfer and a hydrogen evolution reaction kinetics are promoted, so that a catalytic performance of the platinum iron nickel copper catalytic material is significantly improved, which is reflected in that a catalytic performance of the platinum iron nickel copper catalytic material in an alkaline electrolyte is lower than commercial Pt/C, while a catalytic performance of the cobalt-doped platinum iron nickel copper alloy hydrogen evolution catalyst in the alkaline electrolyte exceeds commercial Pt/C and the platinum iron copper catalytic kinetics, and the present application solves the problems of a multi-based hydrogen evolution technology of the existing platinum-doped iron nickel copper alloy hydrogen evolution technology that a hydrogen evolution catalyst has a weaker catalytic performance than commercial Pt/C catalytic hydrogen evolution and a platinum-doped platinum-iron copper catalytic alloy.
Drawings
In order to more clearly illustrate the detailed description of the present application or the technical solutions in the prior art, the drawings used in the detailed description or the prior art description will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an X-ray diffraction pattern of a cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst provided in example 2 of the present application;
FIG. 2 is an electron microscope image of a cobalt-doped Pt-Fe-Ni-Cu alloy hydrogen evolution catalyst provided in example 2 of the present application;
fig. 3 is a graph of hydrogen evolution performance of the cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst in an alkaline electrolyte according to embodiment 2 of the present application;
FIG. 4 is an I-t curve measured at a constant potential of 27mV for the cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst provided in example 2 of the present application.
Detailed Description
The application provides a cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst, a preparation method and a hydrogen fuel cell, which are used for solving the technical problems of weaker hydrogen evolution reaction kinetics and lower hydrogen evolution catalytic performance of a platinum-based multi-element solid solution alloy in the prior art.
The technical solutions of the present application will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.
Example 1
The embodiment 1 of the application provides a cobalt-doped platinum iron nickel copper alloy hydrogen evolution catalyst, and the cobalt-doped platinum iron nickel copper alloy hydrogen evolution catalyst comprises a carrier and cobalt-doped platinum iron nickel copper solid solution alloy particles loaded on the carrier. The X-ray diffraction pattern of the cobalt-doped platinum iron nickel copper solid solution alloy particles is shown in figure 1, the X-ray diffraction pattern can be seen from a metal elementary standard card and a characteristic diffraction peak of the platinum iron nickel copper alloy in the pattern, the cobalt-doped platinum iron nickel copper solid solution alloy particles comprise cobalt, platinum, iron, nickel and copper atoms, and the cobalt, platinum, iron, nickel and copper atoms form a solid solution alloy; further, the characteristic diffraction peaks of the catalyst material platinum iron nickel copper alloy not subjected to cobalt doping are mainly located at 42.03 °, 48.74 °, 71.07 ° and 85.70 °, and the characteristic diffraction peaks of the catalyst material platinum iron nickel copper alloy subjected to cobalt doping are mainly located at 41.52 °, 48.22 °, 70.37 ° and 85.20 °, which indicates that Pt is doped due to Co atoms 4 Metal characteristic peak of X-ray diffraction of FeCoNiCu/CNT catalyst relative to Pt 4 The FeNiCu/CNT are all shifted slightly in the negative direction.
Meanwhile, electron microscope analysis is carried out on the cobalt-doped platinum iron nickel copper alloy hydrogen evolution catalyst, and the result is shown in fig. 2, and as can be seen from fig. 2, the cobalt-doped platinum iron nickel copper solid solution alloy particles are cubic particles and are loaded on the carbon nano tube, and the cobalt-doped platinum iron nickel copper solid solution alloy particles do not agglomerate and can maintain the catalytic activity, and the particle size is about 5-15 nm.
Mass ratio of each atom and atomic mole ratio of each atom in cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst
Shown in table 1.
As can be seen from table 1, the cobalt doping amount of the cobalt doped platinum iron nickel copper alloy hydrogen evolution catalyst provided by the application is small, and the hydrogen evolution catalytic performance of the cobalt doped platinum iron nickel copper alloy can be higher than that of commercial Pt/C under the condition of small amount of doping, which indicates that the catalytic performance of the platinum iron nickel copper catalytic material is significantly improved by cobalt doping.
Example 2
An embodiment 2 of the present application provides a preparation method of the cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst described in embodiment 1, and the preparation method includes a preparation step of a mixed solution containing hexadecyl ammonium chloride and oleylamine, a preparation step of a dispersion liquid containing a metal organic compound, glucose, molybdenum hexacarbonyl, and a carrier, a step of a normal pressure heating reaction, and a post-treatment step.
The preparation method of the mixed solution containing the hexadecyl ammonium chloride and the oleylamine comprises the steps of dissolving 100mg of hexadecyl ammonium chloride (CTAC) in 20mL of Oleylamine (OAM), and carrying out ultrasonic treatment for 15mins to obtain a dispersion liquid, wherein the dispersion liquid is the mixed solution containing the hexadecyl ammonium chloride and the oleylamine.
The preparation of the dispersion containing the metal organic compound, glucose, molybdenum hexacarbonyl and the carrier comprises weighing platinum acetylacetonate 15mg, iron acetylacetonate 3.37mg, cobalt acetylacetonate 3.40mg, nickel acetylacetonate 2.45mg, copper acetylacetonate 2.5mg, carbon Nanotube (CNT) 38.79mg, glucose 60mg and Mo (CO) 6 30mg of the mixture is added into a flask together, and ultrasonic treatment is carried out for 3 hours to obtain dispersion liquid, namely the dispersion liquid containing the metal organic compound, glucose, molybdenum hexacarbonyl and the carrier.
The step of normal pressure heating reaction comprises the steps of adding a mixed solution containing hexadecyl ammonium chloride and oleylamine and a dispersion liquid containing a metal organic compound, glucose, molybdenum hexacarbonyl and a carrier into an oil bath pot, heating and stirring, wherein the oil bath temperature is 220 ℃, and the heating and stirring time is 2 hours, so that the cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst to be treated is obtained.
The post-treatment step comprises: and (2) centrifugally collecting and drying the cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst to be treated by using cyclohexane/ethanol, heating the cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst by using 0.5M acetic acid-alcohol solution at 45 ℃ for 4 hours in an acid bubble mode, washing the catalyst by using ethanol for several times, and drying the catalyst in vacuum at 60 ℃ to obtain the cubic cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst in the embodiment 1. As can be seen from the electron microscope image shown in fig. 2, the preparation method provided by the application has a simple flow, is different from the conventional complex process of firstly preparing catalyst particles and then loading the catalyst particles on a carrier, and can prepare the cubic cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst by carrying out one-pot reaction on the carbon nano tube, the hexadecyl ammonium chloride, the oleylamine, the metal-containing organic compound, the glucose and the molybdenum hexacarbonyl, and the cubic cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst has high catalytic activity and good catalytic stability and can maintain the catalytic activity for a long time (more than 6 hours) compared with the conventional spherical catalyst particles.
Example 3
The embodiment 3 of the application provides a preparation method of a platinum-iron-nickel-copper alloy hydrogen evolution catalyst, and the preparation method comprises a preparation step of a mixed solution containing hexadecyl ammonium chloride and oleylamine, a preparation step of a dispersion liquid containing a metal organic compound, glucose, molybdenum hexacarbonyl and a carrier, a step of heating reaction at normal pressure and a post-treatment step.
The preparation method of the mixed solution containing the hexadecyl ammonium chloride and the oleylamine comprises the steps of dissolving 100mg of hexadecyl ammonium chloride (CTAC) in 20mL of Oleylamine (OAM), and carrying out ultrasonic treatment for 15mins to obtain a dispersion liquid, wherein the dispersion liquid is the mixed solution containing the hexadecyl ammonium chloride and the oleylamine.
The preparation of the dispersion containing the metal organic compound, glucose, molybdenum hexacarbonyl and the carrier comprises weighing platinum acetylacetonate 15mg, iron acetylacetonate 3.37mg, nickel acetylacetonate 2.45mg, copper acetylacetonate 2.5mg, carbon Nanotube (CNT) 38.79mg, glucose 60mg and Mo (CO) 6 30mg of the mixture is added into a flask together, and ultrasonic treatment is carried out for 3 hours to obtain dispersion liquid, namely the dispersion liquid containing the metal organic compound, glucose, molybdenum hexacarbonyl and the carrier.
The step of normal pressure heating reaction comprises the steps of adding a mixed solution containing hexadecyl ammonium chloride and oleyl amine and a dispersion liquid containing a metal organic compound, glucose, molybdenum hexacarbonyl and a carrier into an oil bath pan, heating and stirring, wherein the oil bath temperature is 220 ℃, and the heating and stirring time is 2 hours, so as to obtain the doped platinum iron nickel copper alloy hydrogen evolution catalyst to be treated.
The post-treatment comprises the following steps: and (3) centrifuging, collecting and drying the to-be-treated doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst by using cyclohexane/ethanol, heating the catalyst by using 0.5M acetic acid alcohol solution at 45 ℃ in an acid bubble manner for 4 hours, washing the catalyst by using ethanol for several times, and drying the catalyst in vacuum at 60 ℃ to obtain the platinum-iron-nickel-copper alloy hydrogen evolution catalyst.
Example 4
Embodiment 4 of the present application provides a hydrogen fuel cell, which includes a bipolar plate and membrane electrodes on both sides thereof; the membrane electrode comprises a proton exchange membrane, a catalyst layer and a diffusion layer which are sequentially superposed; the catalyst layer comprises the cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst.
The hydrogen fuel cell provided by the embodiment adopts the catalyst with high catalytic activity and good stability, so that a large amount of hydrogen energy can be provided for a long time, and the hydrogen fuel cell has potential application value.
Test example
The present test example was used to test the hydrogen evolution overpotential and the constant potential current change of the platinum iron nickel copper alloy hydrogen evolution catalyst provided in example 3, the commercial Pt/C, and the cobalt-doped platinum iron nickel copper alloy hydrogen evolution catalyst provided in example 2 in a 1M sodium hydroxide electrolyte.
The hydrogen evolution overpotential and potentiostatic current variation tests were carried out in a standard three-electrode system on an electrochemical workstation of type CHI-750E and in 1M KOH solution, with graphite rods and Hg/HgO electrodes being used as counter and reference electrodes, respectively, and the results are shown in FIGS. 3-4.
FIG. 3 shows hydrogen evolution overpotentials of the Pt-Fe-Ni-Cu alloy hydrogen evolution catalyst provided in example 3, the commercial Pt/C catalyst and the Co-doped Pt-Fe-Ni-Cu alloy hydrogen evolution catalyst provided in example 2 in a 1M sodium hydroxide electrolyte, and it can be seen from FIG. 3 that the current density is 10mA/cm 2 When the overpotential of hydrogen evolution of the platinum iron nickel copper alloy hydrogen evolution catalyst is 58mV, which is higher than 34mV of commercial Pt/C, the higher the overpotential is, the more difficult the hydrogen gas isThe hydrogen evolution catalytic activity of the platinum iron nickel copper alloy hydrogen evolution catalyst is lower than that of commercial Pt/C, while the overpotential of the platinum iron nickel copper alloy hydrogen evolution catalyst provided by the application example 3 is 27mV and is lower than 34mV of the commercial Pt/C, which means that the hydrogen evolution catalytic activity of the cobalt-doped platinum iron nickel copper alloy hydrogen evolution catalyst obtained by doping a small amount of cobalt to the platinum iron nickel copper alloy hydrogen evolution catalyst is higher than that of the commercial Pt/C, the cobalt doping can enable the platinum iron nickel copper catalytic material to deviate from the Fermi level, the interaction between the catalyst and the surface adsorbent is weakened, the material transfer and the hydrogen evolution reaction kinetics are promoted, the catalytic performance of the platinum iron nickel copper catalytic material is obviously improved and exceeds that of the commercial Pt/C.
The current change result at constant potential is shown in fig. 4, and it can be seen from the I-t curve measured at constant potential (over potential is 27 mV) shown in fig. 4 that the cobalt doping provided in example 2 of the present application enables the platinum iron nickel copper catalytic material to have good catalytic stability, and the current does not significantly attenuate in a test of nearly 6 hours, which indicates that the cubic cobalt doped platinum iron nickel copper alloy hydrogen evolution catalyst prepared by reacting the carrier carbon nanotube, hexadecyl ammonium chloride, oleyl amine, the metal-containing organic compound, glucose and molybdenum hexacarbonyl in one pot not only simplifies the preparation process, but also has good catalytic stability, and can maintain the catalytic activity for a long time.
The above embodiments are only used to illustrate the technical solutions of the present application, and not to limit the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Claims (10)
1. The cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst is characterized by comprising a carrier and cobalt-doped platinum-iron-nickel-copper solid solution alloy particles;
the carrier supports the cobalt-doped platinum-iron-nickel-copper solid solution alloy particles.
2. The cobalt-doped platinum iron nickel copper alloy hydrogen evolution catalyst according to claim 1, wherein the cobalt-doped platinum iron nickel copper solid solution alloy particles are cubic particles.
3. The cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst according to claim 2, wherein the particle size of the cobalt-doped platinum-iron-nickel-copper solid solution alloy particles is 5-15 nm.
4. The cobalt-doped platinum iron nickel copper alloy hydrogen evolution catalyst according to claim 3, wherein the carrier is a carbon nanotube.
5. The cobalt-doped platinum iron nickel copper alloy hydrogen evolution catalyst as claimed in claim 1, wherein the atomic ratio of platinum, iron, cobalt, nickel and copper in the cobalt-doped platinum iron nickel copper solid solution alloy particles is 56.04:6.31:0.42:14.17:23.06.
6. the preparation method of the cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst as claimed in any one of claims 1 to 5, wherein the preparation method comprises the steps of: adding a mixed solution containing hexadecyl ammonium chloride and oleylamine into a dispersion liquid containing a metal organic compound, glucose, molybdenum hexacarbonyl and a carrier, and carrying out normal-pressure heating reaction to obtain a cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst;
the metal organic compound comprises platinum acetylacetonate, iron acetylacetonate, cobalt acetylacetonate, nickel acetylacetonate and copper acetylacetonate.
7. The method for preparing the cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst according to claim 6, wherein the temperature of the normal-pressure heating reaction is 150-250 ℃ and the time is 1-4 hours.
8. The preparation method of the cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst according to claim 6, wherein the preparation method of the mixed solution containing the hexadecyl ammonium chloride and the oleylamine comprises the steps of dissolving the hexadecyl ammonium chloride in the oleylamine, and then performing ultrasonic treatment to obtain the mixed solution containing the hexadecyl ammonium chloride and the oleylamine.
9. The method for preparing the cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst according to claim 6, wherein the method for preparing the dispersion liquid containing the metal organic compound, glucose, molybdenum hexacarbonyl and the carrier comprises mixing the metal organic compound, glucose, molybdenum hexacarbonyl and the carrier, and then performing ultrasonic treatment to obtain the dispersion liquid containing the metal organic compound, glucose, molybdenum hexacarbonyl and the carrier.
10. A hydrogen fuel cell is characterized by comprising a bipolar plate and membrane electrodes on two sides of the bipolar plate;
the membrane electrode comprises a proton exchange membrane, a catalyst layer and a diffusion layer which are sequentially superposed;
the catalyst layer comprises the cobalt-doped platinum-iron-nickel-copper alloy hydrogen evolution catalyst.
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| CN116892035A (en) * | 2023-06-28 | 2023-10-17 | 深圳市氢蓝时代动力科技有限公司 | Catalyst for preparing hydrogen for fuel cell and application thereof |
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| CN108232210A (en) * | 2018-01-18 | 2018-06-29 | 兰州交通大学 | A kind of high stability, low-load amount ultra-dispersed noble metal electrocatalyst preparation method |
| CN114917928A (en) * | 2022-04-29 | 2022-08-19 | 华南理工大学 | Star-shaped multifunctional electrocatalytic material of platinum-iron-nickel-copper-ruthenium multi-element alloy solid solution and preparation and application thereof |
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| CN108232210A (en) * | 2018-01-18 | 2018-06-29 | 兰州交通大学 | A kind of high stability, low-load amount ultra-dispersed noble metal electrocatalyst preparation method |
| CN114917928A (en) * | 2022-04-29 | 2022-08-19 | 华南理工大学 | Star-shaped multifunctional electrocatalytic material of platinum-iron-nickel-copper-ruthenium multi-element alloy solid solution and preparation and application thereof |
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| CN116892035A (en) * | 2023-06-28 | 2023-10-17 | 深圳市氢蓝时代动力科技有限公司 | Catalyst for preparing hydrogen for fuel cell and application thereof |
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