CN111621808A - Quaternary high-entropy foam for high-activity electrolyzed water and preparation method thereof - Google Patents
Quaternary high-entropy foam for high-activity electrolyzed water and preparation method thereof Download PDFInfo
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- 239000006260 foam Substances 0.000 title claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 230000000694 effects Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 210000001787 dendrite Anatomy 0.000 claims description 27
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 16
- 239000001509 sodium citrate Substances 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 15
- 230000008021 deposition Effects 0.000 claims description 15
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 12
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 11
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 8
- 238000004070 electrodeposition Methods 0.000 claims description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 abstract description 20
- 239000001301 oxygen Substances 0.000 abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 11
- 239000001257 hydrogen Substances 0.000 abstract description 11
- 239000000956 alloy Substances 0.000 abstract description 8
- 229910045601 alloy Inorganic materials 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229910052738 indium Inorganic materials 0.000 abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 description 9
- 230000004913 activation Effects 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/657—Pore diameter larger than 1000 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses a quaternary high-entropy foam for high-activity electrolyzed water, which belongs to the technical field of micro-nano material preparation and comprises the components of Cu, Ni, Co and Fe, wherein the content of Cu is 23-27 at%, the content of Ni is 23-27 at%, the content of Co is 23-27 at%, and the content of Fe is 23-27 at%. The invention also discloses a preparation method of the composition. The quaternary high-entropy foam for high-activity electrolyzed water has good catalytic activity, can be used In a high-efficiency electrolyzed water technology, and when being used as a catalyst for hydrogen production from water, the surface oxygen evolution overpotential of the NiCuCoFe high-entropy alloy foam prepared by the method can be as low as 250mV, which is far lower than the level of a common high-entropy alloy strip, a film and the surface and is also lower than the level of a commercially available Ru and In oxide catalyst; the preparation method of the invention does not need harsh environments such as high temperature, vacuum and the like in the preparation process, can prepare the finished product within 5 minutes, and has simple and reliable method and low price of raw materials.
Description
Technical Field
The invention belongs to the technical field of micro-nano material preparation, and particularly relates to quaternary high-entropy foam for high-activity electrolyzed water and a preparation method thereof.
Background
The electrolyzed water can simultaneously provide hydrogen and oxygen, and the combination of the hydrogen and the oxygen can generate clean water and simultaneously provide high-density energy, thereby providing a good way for sustainable development and utilization of clean and efficient energy.
However, when the electrolyzed water is used for hydrogen/oxygen evolution, the equilibrium potential is very negative/positive, and the overpotential is very large, especially at the oxygen evolution end, the overpotential is often more than 300 mV. This makes it urgently necessary to use a highly efficient catalyst for water decomposition on the electrode material.
Among the materials developed at present, the most effective hydrogen evolution end is the Pt-based catalyst, and the oxygen evolution end is the oxide of Ru or In. However, such materials are very expensive due to the use of rare metals.
In recent years, non-noble metals and novel carbon-based nano-catalysts are continuously developed to reduce the cost of electrolyzed water. However, most of the materials have the problems of complex preparation process, difficult multi-element doping, large over potential of an oxygen evolution end and the like.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a quaternary high-entropy foam for high-activity electrolyzed water, which has good catalytic activity and can be used for a high-efficiency water electrolysis technology; the invention also aims to provide a preparation method of the quaternary high-entropy foam for high-activity electrolyzed water, which can prepare the quaternary high-entropy foam for high-catalytic-activity electrolyzed water within 5 minutes without harsh conditions such as high temperature, vacuum and the like; the preparation method is simple, and the CuNiCoFe high-entropy alloy prepared by the method has both nano dendrites and a hierarchical porous structure.
The technical scheme is as follows: in order to achieve the purpose, the invention adopts the following technical scheme:
a quaternary high-entropy foam for high-activity electrolyzed water comprises Cu, Ni, Co and Fe, wherein the Cu content is 23-27 at%, the Ni content is 23-27 at%, the Co content is 23-27 at%, and the Fe content is 23-27 at%.
Furthermore, the quaternary high-entropy foam for the high-activity electrolyzed water has three-dimensionally communicated micropores, and the pore diameter of the micropores is within the range of 10-50 um.
Furthermore, the pore wall of the micron pore is composed of CuNiCoFe dendrites.
Further, the length of the primary dendrite of the CuNiCoFe dendrite is 2-3 um, and the length of the higher dendrite is 5-10 nm.
Further, the preparation method of the quaternary high-entropy foam for high-activity electrolyzed water comprises the following steps:
1) placing the working electrode in CuSO4、NiSO4、CoSO4、Fe2(SO4)3、(NH4)2SO4、Na3C6H5O7And H3BO3Mixing the solution;
2) and carrying out constant-current electrochemical deposition.
Further, in step 1), the CuSO4The concentration is 0.003-0.070M, the NiSO4The concentration of (a) is 0.008-0.210M, and the CoSO4The concentration is 0.005-0.15M, and the Fe2(SO4)3The concentration of (A) is 0.008 to 0.12M, the (NH)4)2SO4The concentration is 0.4-0.6M, the Na3C6H5O7The concentration is 0.2-0.4M, the concentration of H3BO3The concentration is 0.3-0.5M.
Further, in step 2), the constant current deposition is carried outThe flow density is 0.7 to 1.2A/cm2The deposition time is 30-3000 s.
Has the advantages that: compared with the prior art, the quaternary high-entropy foam for high-activity water electrolysis has good catalytic activity, can be used for high-efficiency water electrolysis technology, and when the quaternary high-entropy foam is used as a water hydrogen production catalyst, the surface oxygen evolution overpotential of the NiCuCoFe high-entropy alloy foam prepared by the method can be as low as 250mV, which is far lower than the level of a common high-entropy alloy strip, a film and the surface and is also lower than the level of a commercially available Ru and In oxide catalyst; the preparation method of the invention does not need harsh environments such as high temperature, vacuum and the like in the preparation process, can prepare the finished product within 5 minutes, and has simple and reliable method and low price of raw materials.
Drawings
FIG. 1 is a low-power (inset) and high-power topography (scanning electron microscope) of CuNiCoFe high-entropy alloy foam;
FIG. 2 is a CuNiCoFe high-entropy alloy foam energy spectrum;
FIG. 3 is a linear scanning diagram of oxygen evolution reaction on the surface of CuNiCoFe high-entropy alloy foam.
Detailed Description
The invention is further described with reference to the following figures and specific examples.
A quaternary high-entropy foam for high-activity electrolyzed water comprises Cu, Ni, Co and Fe, wherein the Cu content is 23-27 at%, the Ni content is 23-27 at%, the Co content is 23-27 at%, and the Fe content is 23-27 at%.
The foam has a large number of three-dimensionally communicated micropores, and the pore diameter is within the range of 10-50 um.
The hole wall is composed of CuNiCoFe dendrites, the length of the primary dendrite is about 2-3 um, and the length of the higher dendrite is 5-10 nm.
A preparation method of quaternary high-entropy foam for high-activity electrolyzed water comprises the following steps:
1) placing the working electrode in CuSO4、NiSO4、CoSO4、Fe2(SO4)3、(NH4)2SO4、Na3C6H5O7And H3BO3Mixing the solution;
2) and carrying out constant-current electrochemical deposition.
In step 1), CuSO4The concentration is 0.003-0.070M, NiSO4The concentration of (A) is 0.008-0.210M, CoSO4The concentration of Fe is 0.005-0.15M2(SO4)3The concentration of (A) is 0.008-0.12M, (NH)4)2The concentration of SO4 is 0.4-0.6M, Na3C6H5O7The concentration is 0.2-0.4M, H3BO3The concentration is 0.3-0.5M.
In the step 2), the current density of the constant-current deposition is 0.7-1.2A/cm2The deposition time is 30-3000 s.
Example 1
Placing the working electrode in CuSO4、NiSO4、CoSO4、Fe2(SO4)3、(NH4)2SO4、Na3C6H5O7And H3BO3Performing constant-current electrochemical deposition in the mixed solution; CuSO in mixed solution4Concentration of 0.007M, NiSO4In a concentration of 0.010M, CoSO4At a concentration of 0.006M, Fe2(SO4)3Has a concentration of (NH) of 0.005M4)2SO4The concentration is 0.5M, Na3C6H5O7At a concentration of 0.3M, H3BO3The concentration is 0.4M; the deposition time is 3000s, and the deposition current is 0.7A/cm2。
The foam prepared by the above procedure was composed of Cu, Ni, Co and Fe, in which the Cu content was 25 at%, the Ni content was 25 at%, the Co content was 25 at%, and the Fe content was 25 at% (as shown in fig. 1, composition information was obtained by energy dispersive spectroscopy). The foam has a large number of three-dimensionally communicated micropores, and the pore diameter is within the range of 25-50 um. The hole wall is composed of CuNiCoFe dendrites, the length of the primary dendrite is about 2um, the length of the higher dendrite is between 5 nm and 7nm, and the specific structure diagram is shown in figure 2.
After activation, the overpotential for hydrogen evolution on the surface of the foam is 80mV and the overpotential for oxygen evolution is 250 mV. Oxygen evolution overpotential measurements are shown in figure 3:gradually increasing the potential of the measured sample from 1.2V to 1.6V, and simultaneously measuring the current passing through the sample to obtain a potential-current curve; when the current density reaches 10mA/cm2When the corresponding potential is the actual oxygen evolution potential; the difference between the actual oxygen evolution potential and the theoretical oxygen evolution potential is the oxygen evolution overpotential.
Example 2
Placing the working electrode in CuSO4、NiSO4、CoSO4、Fe2(SO4)3、(NH4)2SO4、Na3C6H5O7And H3BO3Performing constant-current electrochemical deposition in the mixed solution; CuSO in mixed solution4Concentration of 0.070M, NiSO4In a concentration of 0.210M, CoSO4Concentration of 0.150M, Fe2(SO4)3Has a concentration of (NH) of 0.120M4)2SO4The concentration is 0.4M, Na3C6H5O7At a concentration of 0.2M, H3BO3The concentration is 0.3M; the deposition time was 60s, and the deposition current was 1.2A/cm2。
The foam prepared by the above steps consists of Cu, Ni, Co and Fe, wherein the Cu content is 23 at%, the Ni content is 23 at%, the Co content is 27 at%, and the Fe content is 27 at%. The foam has a large number of three-dimensionally communicated micropores, and the pore diameter is within the range of 30-50 um. The hole wall is composed of CuNiCoFe dendrites, the length of the primary dendrite is about 3um, and the length of the higher dendrite is between 5 and 10 nm.
After activation, the overpotential for hydrogen evolution on the surface of the foam is 90mV and the overpotential for oxygen evolution is 290 mV.
Example 3
Placing the working electrode in CuSO4、NiSO4、CoSO4、Fe2(SO4)3、(NH4)2SO4、Na3C6H5O7And H3BO3And carrying out constant-current electrochemical deposition in the mixed solution. CuSO4Concentration of 0.003M, NiSO4Is 0.008M, CoSO4At a concentration of 0.005M, Fe2(SO4)3Is 0.008M: (NH4)2SO4The concentration is 0.6M, Na3C6H5O7At a concentration of 0.4M, H3BO3The concentration was 0.5M. The current density of the deposit is 1.2A/cm2The deposition time was 3000 s.
The foam prepared by the steps consists of Cu, Ni, Co and Fe, wherein the Cu content is 27 at%, the Ni content is 27 at%, the Co content is 23 at%, and the Fe content is 23 at%. The foam has a large number of three-dimensionally communicated micropores, and the pore diameter is within the range of 10-50 um. The hole wall is composed of CuNiCoFe dendrites, the length of the primary dendrite is about 2-3 um, and the length of the higher dendrite is 5-10 nm.
After activation, the overpotential for hydrogen evolution on the surface of the foam is 87mV and the overpotential for oxygen evolution is 270 mV.
Example 4
Placing the working electrode in CuSO4、NiSO4、CoSO4、Fe2(SO4)3、(NH4)2SO4、Na3C6H5O7And H3BO3Performing constant-current electrochemical deposition in the mixed solution; CuSO in mixed solution4Concentration of 0.030M, NiSO4In a concentration of 0.100M, CoSO4At a concentration of 0.060M, Fe2(SO4)3Has a concentration of (NH) of 0.050M4)2SO4The concentration is 0.5M, Na3C6H5O7At a concentration of 0.3M, H3BO3The concentration is 0.4M; the deposition time was 60s, and the deposition current was 1.0A/cm2。
The foam prepared by the above steps consists of Cu, Ni, Co and Fe, wherein the Cu content is 23 at%, the Ni content is 25 at%, the Co content is 26 at%, and the Fe content is 26 at%. The foam has a large number of three-dimensionally communicated micropores, and the pore diameter is within the range of 25-50 um. The hole wall is composed of CuNiCoFe dendrites, the length of the primary dendrite is about 3um, and the length of the higher dendrite is between 5 and 10 nm.
After activation, the overpotential for hydrogen evolution on the surface of the foam is 75mV and the overpotential for oxygen evolution is 260 mV. The oxygen evolution overpotential measurement method is shown in fig. 3.
Example 5
Placing the working electrode in CuSO4、NiSO4、CoSO4、Fe2(SO4)3、(NH4)2SO4、Na3C6H5O7And H3BO3Performing constant-current electrochemical deposition in the mixed solution; CuSO in mixed solution4Concentration of 0.030M, NiSO4In a concentration of 0.100M, CoSO4At a concentration of 0.060M, Fe2(SO4)3Has a concentration of (NH) of 0.050M4)2SO4The concentration is 0.5M, Na3C6H5O7At a concentration of 0.3M, H3BO3The concentration is 0.4M; the deposition time was 30s and the deposition current was 1.0A/cm2。
The foam prepared by the above steps consists of Cu, Ni, Co and Fe, wherein the Cu content is 23 at%, the Ni content is 25 at%, the Co content is 26 at%, and the Fe content is 26 at%. The foam has a large number of three-dimensionally communicated micropores, and the pore diameter is within the range of 10-20 um. The hole wall is composed of CuNiCoFe dendrites, the length of the primary dendrite is about 2um, and the length of the higher dendrite is between 5 and 7 nm.
After activation, the overpotential for hydrogen evolution on the surface of the foam is 82mV and the overpotential for oxygen evolution is 275 mV.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (7)
1. A quaternary high-entropy foam for high-activity electrolyzed water is characterized by comprising Cu, Ni, Co and Fe, wherein the Cu content is 23-27 at%, the Ni content is 23-27 at%, the Co content is 23-27 at%, and the Fe content is 23-27 at%.
2. The quaternary high-entropy foam for high-activity electrolyzed water as defined in claim 1, wherein: the quaternary high-entropy foam for the high-activity electrolyzed water has three-dimensionally communicated micropores, and the pore diameter of the micropores is within the range of 10-50 um.
3. The quaternary high-entropy foam for high-activity electrolyzed water as defined in claim 2, wherein: the pore wall of the micron pore is composed of CuNiCoFe dendrites.
4. The quaternary high-entropy foam for high-activity electrolyzed water as defined in claim 3, wherein: CuNiCoFe dendrite primary dendrite length be 2 ~ 3um, higher dendrite length be 5 ~ 10 nm.
5. The method for preparing the quaternary high-entropy foam for the high-activity electrolyzed water as defined in any one of claims 1 to 4, which is characterized by comprising the following steps:
1) placing the working electrode in CuSO4、NiSO4、CoSO4、Fe2(SO4)3、(NH4)2SO4、Na3C6H5O7And H3BO3Mixing the solution;
2) and carrying out constant-current electrochemical deposition.
6. The method for preparing the quaternary high-entropy foam for the high-activity electrolyzed water as claimed in claim 5, wherein in the step 1), the CuSO is added4The concentration is 0.003-0.070M, the NiSO4The concentration of (a) is 0.008-0.210M, and the CoSO4The concentration is 0.005-0.15M, and the Fe2(SO4)3The concentration of (A) is 0.008 to 0.12M, the (NH)4)2SO4The concentration is 0.4-0.6M, the Na3C6H5O7The concentration is 0.2-0.4M, the concentration of H3BO3The concentration is 0.3-0.5M.
7. The method for preparing the quaternary high-entropy foam for the high-activity electrolyzed water as claimed in claim 5, wherein in the step 2), the quaternary high-entropy foam is preparedThe current density of the constant-current deposition is 0.7-1.2A/cm2The deposition time is 30-3000 s.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112376070A (en) * | 2020-11-30 | 2021-02-19 | 东北大学秦皇岛分校 | Multi-principal-element alloy nano catalyst capable of efficiently separating out oxygen, and preparation method and application thereof |
| CN112609213A (en) * | 2020-12-11 | 2021-04-06 | 东北大学 | High-entropy alloy porous electrode and preparation method thereof |
| CN114808007A (en) * | 2022-03-14 | 2022-07-29 | 青岛科技大学 | Method for preparing Ni-Fe-Cu-Co-W high-entropy alloy electrocatalyst by electrodeposition method |
| CN114836780A (en) * | 2022-05-07 | 2022-08-02 | 东南大学 | Six-element high-entropy foam for hydrogen production by hydrolysis and preparation method thereof |
| CN115142073A (en) * | 2022-08-10 | 2022-10-04 | 天津理工大学 | Preparation and application of FeCoNiCuMn nano high-entropy alloy electrocatalyst |
| CN117230480A (en) * | 2023-11-10 | 2023-12-15 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | High-entropy alloy dual-function electrocatalytic film and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170275745A1 (en) * | 2016-03-11 | 2017-09-28 | The Industry & Academic Cooperation In Chungnam National University (Iac) | High Entropy Alloy Having Composite Microstructure and Method of Manufacturing the Same |
| CN107587158A (en) * | 2017-08-11 | 2018-01-16 | 天津工业大学 | A kind of nanoporous high-entropy alloy electrode and its preparation method and application |
| CN107779620A (en) * | 2017-10-31 | 2018-03-09 | 辽宁工业大学 | A kind of method of regulation and control CoCrFeNiCu high-entropy alloy performances |
| CN109763056A (en) * | 2018-12-24 | 2019-05-17 | 江苏理工学院 | A kind of Fe-Co-Ni-Mn-Cu high entropy alloy material and its preparation process |
| CN110013831A (en) * | 2019-05-05 | 2019-07-16 | 中国矿业大学 | A kind of nanoparticle activated carbon and its preparation method and application of load C oCrCuFeNi high-entropy alloy |
| CN111185188A (en) * | 2019-12-27 | 2020-05-22 | 江南大学 | Iron-cobalt-nickel-copper-based high-entropy alloy electrolytic water catalytic material and preparation method thereof |
-
2020
- 2020-06-22 CN CN202010572610.4A patent/CN111621808B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170275745A1 (en) * | 2016-03-11 | 2017-09-28 | The Industry & Academic Cooperation In Chungnam National University (Iac) | High Entropy Alloy Having Composite Microstructure and Method of Manufacturing the Same |
| CN107587158A (en) * | 2017-08-11 | 2018-01-16 | 天津工业大学 | A kind of nanoporous high-entropy alloy electrode and its preparation method and application |
| CN107779620A (en) * | 2017-10-31 | 2018-03-09 | 辽宁工业大学 | A kind of method of regulation and control CoCrFeNiCu high-entropy alloy performances |
| CN109763056A (en) * | 2018-12-24 | 2019-05-17 | 江苏理工学院 | A kind of Fe-Co-Ni-Mn-Cu high entropy alloy material and its preparation process |
| CN110013831A (en) * | 2019-05-05 | 2019-07-16 | 中国矿业大学 | A kind of nanoparticle activated carbon and its preparation method and application of load C oCrCuFeNi high-entropy alloy |
| CN111185188A (en) * | 2019-12-27 | 2020-05-22 | 江南大学 | Iron-cobalt-nickel-copper-based high-entropy alloy electrolytic water catalytic material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| D. M. F. SANTOS ET AL: "Transition Metal Foam Electrocatalysts for Hydrogen Evolution Reaction", 《ECS TRANSACTIONS》 * |
| L. LIU ET AL: "Microstructure and the properties of FeCoCuNiSnx high entropy alloys", 《MATERIALS SCIENCE AND ENGINEERING A》 * |
| MATTHEW W. GLASSCOTT ET AL: "Electrosynthesis of high-entropy metallic glass nanoparticles for designer, multi-functional electrocatalysis", 《NATURE COMMUNICATIONS》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112376070A (en) * | 2020-11-30 | 2021-02-19 | 东北大学秦皇岛分校 | Multi-principal-element alloy nano catalyst capable of efficiently separating out oxygen, and preparation method and application thereof |
| CN112376070B (en) * | 2020-11-30 | 2021-09-10 | 东北大学秦皇岛分校 | Multi-principal-element alloy nano catalyst capable of efficiently separating out oxygen, and preparation method and application thereof |
| CN112609213A (en) * | 2020-12-11 | 2021-04-06 | 东北大学 | High-entropy alloy porous electrode and preparation method thereof |
| CN114808007A (en) * | 2022-03-14 | 2022-07-29 | 青岛科技大学 | Method for preparing Ni-Fe-Cu-Co-W high-entropy alloy electrocatalyst by electrodeposition method |
| CN114836780A (en) * | 2022-05-07 | 2022-08-02 | 东南大学 | Six-element high-entropy foam for hydrogen production by hydrolysis and preparation method thereof |
| CN114836780B (en) * | 2022-05-07 | 2023-11-03 | 东南大学 | Six-element high-entropy foam for hydrogen production by hydrolysis and preparation method thereof |
| WO2023216592A1 (en) * | 2022-05-07 | 2023-11-16 | 东南大学 | Six-membered high-entropy foam for hydrogen production by hydrolysis and preparation method therefor |
| CN115142073A (en) * | 2022-08-10 | 2022-10-04 | 天津理工大学 | Preparation and application of FeCoNiCuMn nano high-entropy alloy electrocatalyst |
| CN117230480A (en) * | 2023-11-10 | 2023-12-15 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | High-entropy alloy dual-function electrocatalytic film and preparation method and application thereof |
| CN117230480B (en) * | 2023-11-10 | 2024-02-06 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | High-entropy alloy dual-function electrocatalytic film and preparation method and application thereof |
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