CN113215612A - Method for electrolyzing water and method for preparing catalyst for electrolyzing water - Google Patents
Method for electrolyzing water and method for preparing catalyst for electrolyzing water Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 51
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 90
- 239000000956 alloy Substances 0.000 claims abstract description 90
- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 238000009713 electroplating Methods 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 32
- 238000005868 electrolysis reaction Methods 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 16
- 229910017052 cobalt Inorganic materials 0.000 claims description 16
- 239000010941 cobalt Substances 0.000 claims description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims description 16
- 239000011733 molybdenum Substances 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 12
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 10
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 8
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 7
- 239000011609 ammonium molybdate Substances 0.000 claims description 7
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 7
- 229940010552 ammonium molybdate Drugs 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- VSOYJNRFGMJBAV-UHFFFAOYSA-N N.[Mo+4] Chemical compound N.[Mo+4] VSOYJNRFGMJBAV-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000007747 plating Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910001325 element alloy Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
-
- 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
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Catalysts (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
一种电解水的方法及用于电解水的触媒的制备方法。所述电解水的方法包括使用高熵合金作为触媒。此外，所述用于电解水的触媒的制备方法包括以下步骤：将基板置于含高熵合金前体的水系电解液中；对所述基板进行电镀工艺，以于所述基板上形成高熵合金触媒。
A method for electrolyzing water and a method for preparing a catalyst for electrolyzing water. The method for electrolyzing water includes using a high-entropy alloy as a catalyst. In addition, the preparation method of the catalyst for electrolyzing water includes the following steps: placing a substrate in an aqueous electrolyte containing a high-entropy alloy precursor; performing an electroplating process on the substrate to form a high-entropy alloy on the substrate alloy catalyst.
Description
Technical Field
The invention relates to a method for electrolyzing water and a preparation method of a catalyst for electrolyzing water.
Background
In the chemical industry, hydrogen is needed for the synthesis of hydrocarbons, and fossil raw materials (fossils fuel) are generally used as hydrogen production raw materials. However, carbon dioxide is generated during the process of producing hydrogen, and thus carbon dioxide emission is increased to cause environmental pollution. In addition, the process of producing hydrogen is highly dependent on fossil raw materials, so that the method cannot meet the laws of modern industrial development and the concept of continuous development.
BRIEF SUMMARY OF THE PRESENT DISCLOSURE
The invention provides a method for electrolyzing water, which uses a high-entropy alloy as a catalyst.
The invention provides a preparation method of a catalyst for water electrolysis, which forms a high-entropy alloy catalyst on a substrate by using an electroplating process.
The method for electrolyzing water of the present invention uses a high entropy alloy as a catalyst.
In an embodiment of the method of electrolyzing water of the present invention, the high entropy alloy is for example iron, cobalt, nickel, copper and molybdenum, and the content of each of iron, cobalt, nickel, copper and molybdenum is for example between 5 at.% and 35 at.%, based on the total moles of the high entropy alloy.
In an embodiment of the method of electrolyzing water of the present invention, the high entropy alloy is, for example, iron, cobalt, nickel, copper, molybdenum and manganese, and the content of each of iron, cobalt, nickel, copper, molybdenum and manganese is, for example, between 5 at.% and 35 at.%, based on the total moles of the high entropy alloy.
In an embodiment of the method of electrolyzing water of the present invention, an aqueous solution having a pH between 7 and 14 is used as the electrolyte at the anode, for example.
In an embodiment of the method of electrolyzing water of the present invention, an aqueous solution having a pH between 0 and 14 is used as the electrolyte at the cathode, for example.
The preparation method of the catalyst for electrolyzing water comprises the following steps: placing the substrate in an aqueous electrolyte containing a high-entropy alloy precursor; and carrying out an electroplating process on the substrate to form the high-entropy alloy catalyst on the substrate.
In an embodiment of the method for preparing a catalyst for the electrolysis of water according to the present invention, the high entropy alloy precursor is, for example, ferric chloride, cobalt chloride, nickel chloride, cupric chloride and ammonium molybdate.
In an embodiment of the method for preparing a catalyst for electrolyzing water of the present invention, the high entropy alloy precursor is, for example, manganese chloride, ferric chloride, cobalt chloride, nickel chloride, copper chloride and ammonium molybdate.
In an embodiment of the method for preparing a catalyst for electrolyzing water of the present invention, the current density of the electroplating process is, for example, 2A/cm2To 6A/cm2In the meantime.
In an embodiment of the method for preparing a catalyst for electrolyzing water of the present invention, the substrate is, for example, a porous substrate.
In view of the above, in the present invention, the high-entropy alloy is used as a catalyst in water electrolysis, so that the overpotential (overpotential) required for water electrolysis can be effectively reduced to reduce power consumption. In addition, the high-entropy alloy catalyst is formed by an electroplating process, so that the preparation steps of the high-entropy alloy catalyst can be simplified, the preparation cost can be reduced, and the formed high-entropy alloy catalyst can have a larger surface area and can effectively improve the efficiency of water electrolysis.
In order to make the aforementioned and other features and advantages of the invention more comprehensible, embodiments accompanied with figures are described in detail below.
Drawings
Fig. 1 is a flow chart illustrating a method for electrolyzing water according to an embodiment of the present invention.
FIG. 2 is a flowchart of a method for preparing a high-entropy alloy catalyst according to an embodiment of the invention.
FIG. 3 is a Scanning Electron Microscope (SEM) photograph of the quinary high-entropy alloy catalyst of Experimental example 3.
Fig. 4 is a photograph of a Transmission Electron Microscope (TEM) of the quinary high-entropy alloy catalyst of experimental example 3.
FIG. 5 is a scanning electron microscope photograph of the six-membered high-entropy alloy catalyst of Experimental example 4.
FIG. 6 is a transmission electron microscope photograph of a six-membered high entropy alloy catalyst of Experimental example 4.
Detailed Description
Hereinafter, "high entropy alloy" broadly refers to a five-element alloy, a six-element alloy, or a higher-element alloy, and wherein the content of each metal element is between 5 at.% and 35 at.%. That is, these metal elements are the main components of the high-entropy alloy, and the high-entropy alloy may further contain a trace amount of other impurities.
In the invention, the high-entropy alloy is used as a catalyst in water electrolysis, so that the overpotential required by water electrolysis can be reduced, and the electric energy consumption is reduced. In addition, the hydrogen generated by the water electrolysis is used for synthesizing the hydrocarbon, and the fossil raw material is not needed to be used as the hydrogen-generating raw material, so the generation of carbon dioxide can be effectively reduced.
In addition, in the invention, the high-entropy alloy catalyst is formed on the substrate by an electroplating process, so that the preparation steps of the high-entropy alloy catalyst can be simplified and the preparation cost can be reduced. Moreover, because the high-entropy alloy catalyst is formed by adopting an electroplating process, the high-entropy alloy catalyst has a more three-dimensional structure and a larger surface area, and can effectively improve the efficiency of water electrolysis.
The method for electrolyzing water and the method for preparing the catalyst of the present invention will be described below separately.
Fig. 1 is a flow chart illustrating a method for electrolyzing water according to an embodiment of the present invention. Referring to fig. 1, in step 100, an electrode having a high-entropy alloy catalyst formed on a surface thereof is inserted into an electrolyte. In the present embodiment, a quinary high-entropy alloy and a senary high-entropy alloy are used as the catalysts for electrolyzing water, respectively, but the present invention is not limited thereto. In other embodiments, more highly entropic alloys may be used as the water electrolysis catalyst.
In the case of using a quinary high-entropy alloy as a catalyst for electrolyzing water, a high-entropy alloy including iron, cobalt, nickel, copper and molybdenum as main components may be used, but the present invention is not limited thereto. The content of each of iron, cobalt, nickel, copper, and molybdenum is between 5 at.% and 35 at.%, based on the total moles of the pentavalent high entropy alloy. Preferably, the iron, cobalt, nickel, copper and molybdenum may be present in a ratio of 1: 1: 1: 1: the ratio of 1 is present in the quinary high entropy alloy. In this case, the quinary high-entropy alloy catalyst does not contain a noble metal, so that the production cost can be reduced and commercialization is facilitated.
In the case of using a six-membered high-entropy alloy as a catalyst for electrolyzing water, a high-entropy alloy including manganese, iron, cobalt, nickel, copper and molybdenum as main components may be used, but the present invention is not limited thereto. The respective contents of manganese, iron, cobalt, nickel, copper and molybdenum are between 5 at.% and 35 at.%, based on the total moles of the six-membered high entropy alloy. Preferably, the manganese, iron, cobalt, nickel, copper and molybdenum may be present in a ratio of 1: 1: 1: 1: 1: the ratio of 1 is present in six-membered high entropy alloys. In this case, the six-membered high-entropy alloy catalyst does not contain a noble metal, so that the production cost can be reduced and commercialization is facilitated.
In addition, in the present embodiment, the anode and the cathode are inserted into different electrolytes, respectively. In detail, the anode is inserted into an aqueous solution having a pH value between 7 and 14, and the cathode is inserted into an aqueous solution having a pH value between 0 and 14. However, the present invention is not limited thereto. In other embodiments, the anode and cathode may be inserted together into an aqueous solution having a pH between 7 and 14.
In step 102, a voltage is applied to the anode and the cathode to cause an oxidation reaction at the anode and a reduction reaction at the cathode. At this time, oxygen is generated at the anode, and hydrogen is generated at the cathode. The produced hydrogen can be used for synthesizing hydrocarbon, and therefore, fossil raw materials are not needed to be used as hydrogen-producing raw materials. Therefore, carbon emission caused by the generation of carbon dioxide can be avoided. In addition, the high entropy alloy catalyst is formed on the surface of the electrode, so that the overpotential required for water electrolysis can be effectively reduced, and the effect of reducing the electric energy consumption is achieved.
The effect of the present embodiment will be described below with reference to experimental examples.
Experimental example 1
Quinary high-entropy alloy containing iron, cobalt, nickel, copper and molybdenum as main components is used as a catalyst, and 1M potassium hydroxide aqueous solution is used as electrolyte to electrolyze water.
A three-pole measurement system (three electrode system) is adopted, and before the electrochemical polarization curve measurement of Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER) is carried out, a Cyclic Voltammetry (CV) method is used for preliminarily confirming the position of an oxidation-reduction peak, and simultaneously ensuring that the system reaches a stable state, so as to carry out the subsequent experimental steps.
For oxygen evolution reaction measurements, the CV scan range was 0V to 1V (vs. Hg/HgO electrode), for hydrogen evolution reaction measurements, the CV scan range was-0.5V to-1.5V (vs. Hg/HgO electrode), the scan rate was 100mV/s, the scan period was 20 cycles back and forth, and the sensitivity was 0.1A/V. After cyclic voltammetry is completed, the system can measure the oxygen evolution reaction amount and the catalyst overpotential of the hydrogen evolution reaction. The overpotential was measured using iR-corrected Linear Sweep Voltammetry (LSV), which was the same as the cyclic voltammetry of the previous step, but the scanning speed was changed to 0.5mV/s to ensure that the potential at each point reached a stable equilibrium state.
After measurement, the current density is 10mA/cm2Then, the overpotential for generating oxygen is 215mV, and the overpotential for generating hydrogen is 10mV (comparable to platinum catalyst); at a high current density of 500mA/cm2The overpotential for oxygen generation is 292mV, and the overpotential for hydrogen generation is 144 mV. Therefore, the method for electrolyzing water of the embodiment can effectively reduce the overpotential required for electrolyzing water, thereby effectively reducing the power consumption.
Experimental example 2
The electrolysis of water was carried out using a six-membered high-entropy alloy containing manganese, iron, cobalt, nickel, copper and molybdenum as the main components as a catalyst and using a 1M aqueous solution of potassium hydroxide as an electrolyte. The same experimental procedures and measurements as in experimental example 1 were carried out.
For oxygen evolution reaction measurements, the CV scan range was 0V to 1V (vs. Hg/HgO electrode), for hydrogen evolution reaction measurements, the CV scan range was-0.5V to-0.1V (vs. Ag/AgCl electrode), the scan rate was 100mV/s, the scan period was 20 cycles back and forth, and the sensitivity was 0.1A/V.
After measurement, the current density is 10mA/cm2The overpotential for oxygen generation is 201mV, and the overpotential for hydrogen generation is 16 mV; at a high current density of 500mA/cm2The overpotential for oxygen generation is 282mV, and the overpotential for hydrogen generation is 159 mV. Therefore, the method for electrolyzing water of the embodiment can effectively reduce the overpotential required for electrolyzing water, thereby effectively reducing the power consumption.
In addition, the quinary high-entropy alloy catalyst and the senary high-entropy alloy catalyst have excellent effects under the condition that 0.5M sulfuric acid aqueous solution is used as electrolyte. For example, the five-element high-entropy alloy and 0.5M sulfuric acid aqueous solution are used as electrolyte and the current density is 10mA/cm2In the case of (2), the hydrogen production overpotential is only 10 mV; the six-membered high-entropy alloy and 0.5M sulfuric acid aqueous solution are used as electrolyte, and the current density is 10mA/cm2In the case of (2), the hydrogen generation overpotential is only 15 mV.
The preparation method of the high-entropy alloy catalyst will be described below.
FIG. 2 is a flowchart of a method for preparing a high-entropy alloy catalyst according to an embodiment of the invention. Referring to fig. 2, in step 200, a substrate is placed in an aqueous electrolyte containing a high-entropy alloy precursor. In the present embodiment, the substrate is a porous substrate, such as a metal foam skeleton. In addition, in the present embodiment, an aqueous electrolytic solution containing a quinary-element high-entropy alloy precursor and an aqueous electrolytic solution containing a hexabasic high-entropy alloy precursor are used, respectively, but the present invention is not limited thereto. In other embodiments, aqueous electrolytes containing more elemental high entropy alloy precursors may also be used.
In case of using an aqueous electrolyte containing a five-membered high entropy alloy precursor, the five-membered high entropy alloy precursor may be (but is not limited to) ferric chloride, cobalt chloride, nickel chloride, copper chloride and ammonium molybdate, and a chelating agent may be optionally added.
In case of using an aqueous electrolyte containing a six-membered high entropy alloy precursor, the five-membered high entropy alloy precursor may be (but is not limited to) manganese chloride, ferric chloride, cobalt chloride, nickel chloride, copper chloride and ammonium molybdate, and a chelating agent may be optionally added.
In step 202, a plating process is performed on the substrate to form a high-entropy alloy catalyst on the substrate. Thus, the substrate with the high-entropy alloy catalyst formed on the surface can be used as an anode and a cathode in water electrolysis. In the present embodiment, the current density of the electroplating process is, for example, between 2A/cm2To 6A/cm2In the meantime.
In the embodiment, the high-entropy alloy catalyst is formed on the substrate by the electroplating process, so that the preparation steps of the high-entropy alloy catalyst are simplified, and the preparation cost can be lower. In addition, based on the characteristics of the electroplating process, the formed high-entropy alloy catalyst can have a three-dimensional structure and a large surface area, so that the water electrolysis efficiency can be effectively improved.
The preparation method of the high-entropy alloy catalyst of the present invention will be described below with reference to experimental examples.
Experimental example 3
The foamed nickel skeleton (pore density 100PPI) was placed in an aqueous electrolyte containing a five-membered high entropy alloy precursor. The high-entropy alloy precursors in the aqueous electrolyte were ferric chloride (0.3M), cobalt chloride (0.2M), nickel chloride (0.5M), copper chloride (0.005M), and ammonium molybdate (0.045M), and sodium citrate (0.4M) was added as a chelating agent.
Adjusting pH of the electrolyte to 9 with ammonia water, and performing pulse electroplating by bipolar electroplating method with current density of 4A/cm2The plating cycle was 3000 cycles, the plating time (on time) was 0.2 seconds, and the current off time (off time) was 0.8 seconds. After the electroplating, the test piece is cleaned by deionized water and acetone.
FIG. 3 is a scanning electron microscope photograph of the quinary high-entropy alloy catalyst of Experimental example 3. FIG. 4 is a transmission electron microscope photograph of the quinary high-entropy alloy catalyst of Experimental example 3. As is clear from FIG. 3, the five-element high-entropy alloy catalyst has a large number of dendritic structures. In addition, as shown in FIG. 4, the five-element high-entropy alloy catalyst is formed in a face-centered cubic (FCC) structure, and the interplanar spacing of the (111) plane is 0.209nm, and the interplanar spacing of the (220) plane is 0.181 nm.
Experimental example 4
A foamed nickel skeleton (pore density of 100PPI) was placed in an aqueous electrolyte containing a six-membered high entropy alloy precursor. The high-entropy alloy precursors in the aqueous electrolyte were manganese chloride (0.4M), iron chloride (0.3M), cobalt chloride (0.05M), nickel chloride (0.5M), copper chloride (0.002M), and ammonium molybdate (0.02M), respectively, and sodium citrate (0.4M) was added as a chelating agent.
Adjusting pH of the electrolyte to 9 with ammonia water, and performing pulse electroplating by bipolar electroplating method with current density of 4A/cm2The plating cycle was 3000 cycles, the plating time was 0.2 seconds, and the current stop time was 0.8 seconds. After the electroplating, the test piece is cleaned by deionized water and acetone.
FIG. 5 is a scanning electron microscope photograph of the six-membered high-entropy alloy catalyst of Experimental example 4. FIG. 6 is a transmission electron microscope photograph of a six-membered high entropy alloy catalyst of Experimental example 4. As is clear from fig. 5, the six-membered high entropy alloy formed has a large number of dendritic structures. In addition, as shown in FIG. 6, the six-membered high-entropy alloy formed was of a face-centered cubic structure, and the interplanar spacing of the (111) planes was 0.208nm and the interplanar spacing of the (200) planes was 0.179 nm.
Although the present invention has been described with reference to the above embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
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