CN114534738B - Metal manganese or manganese alloy catalyst and manufacturing method thereof - Google Patents
Metal manganese or manganese alloy catalyst and manufacturing method thereof Download PDFInfo
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- CN114534738B CN114534738B CN202011361322.0A CN202011361322A CN114534738B CN 114534738 B CN114534738 B CN 114534738B CN 202011361322 A CN202011361322 A CN 202011361322A CN 114534738 B CN114534738 B CN 114534738B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 63
- 239000002184 metal Substances 0.000 title claims abstract description 63
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000011572 manganese Substances 0.000 title claims abstract description 36
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 36
- 229910000914 Mn alloy Inorganic materials 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000009713 electroplating Methods 0.000 claims abstract description 35
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000007747 plating Methods 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 12
- 150000003863 ammonium salts Chemical class 0.000 claims description 9
- 150000002696 manganese Chemical class 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 6
- DPGAAOUOSQHIJH-UHFFFAOYSA-N ruthenium titanium Chemical compound [Ti].[Ru] DPGAAOUOSQHIJH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002086 nanomaterial Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000007772 electrode material Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 229910052802 copper Inorganic materials 0.000 description 16
- 239000010949 copper Substances 0.000 description 16
- 229910000531 Co alloy Inorganic materials 0.000 description 12
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 12
- 229910018669 Mn—Co Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910020212 Na2SnO3 Inorganic materials 0.000 description 1
- 229910018162 SeO2 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910002064 alloy oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
-
- 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
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
-
- 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
- C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
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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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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- 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
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Abstract
The invention provides a structure of a metal manganese or manganese alloy catalyst and a manufacturing method thereof. The metal manganese or manganese alloy catalyst has a porous structure, and the pore wall of the porous structure is metal manganese or manganese alloy, or a mixture of metal manganese and manganese oxide, or a mixture of manganese alloy and manganese alloy oxide. The catalyst is manufactured by adopting an electroplating method. The catalyst has the advantages of simple manufacturing process and high production efficiency, and can greatly improve the effective reaction area of the catalyst. In particular, the catalyst is used as an electrode material, can obviously reduce the resistance and improve the electrode performance.
Description
Technical Field
The invention belongs to the field of functional materials. In particular to a metal manganese or manganese alloy catalyst structure and a manufacturing method thereof.
Background
The metal manganese and manganese alloy used as the catalyst and the oxide of the metal manganese and manganese alloy are widely applied in the fields of materials, chemical industry and energy sources. At present, the catalyst generally adopts powder or adopts an adhesive to adhere the powder on the surface of a matrix material. The catalytic reaction proceeds on the surface of the catalyst, and therefore, the larger the contact area between the catalyst surface and the reactant is, the better the catalytic reaction effect is. By adopting the powder catalyst, the accumulation among the catalyst powder can greatly reduce the effective area of the catalyst surface for catalytic reaction. When the catalyst of the powder is adhered to the surface of a base material through an adhesive to be used as an electrocatalyst of an electrode material, the resistance is increased, and the electrode performance is reduced.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a metal manganese or manganese alloy catalyst which is of a porous structure, wherein the pore wall of the porous structure is of metal manganese or manganese alloy, or a mixture of metal manganese and manganese oxide, or a mixture of manganese alloy and manganese alloy oxide.
Still further, the method comprises the steps of,
The surface of the pore wall of the catalyst is also provided with micro-protrusions with nano structures.
The pore wall surface of the catalyst is coated with manganese oxide or manganese alloy oxide.
In order to solve the problems in the prior art, the invention also provides a manufacturing method of the metal manganese or manganese alloy catalyst, which comprises the following steps:
The plating method is adopted for manufacturing: taking a conductive substrate as a cathode, and taking a metal manganese or manganese alloy or ruthenium-titanium mesh or platinum-plated titanium mesh or titanium mesh as an anode, and placing the anode into an electrolytic tank; the cathode and the anode are respectively connected with the cathode and the anode of the power supply; controlling current density, and electroplating metal manganese or manganese alloy with a porous structure or a mixture of metal manganese and manganese oxide or a mixture of manganese alloy and manganese alloy oxide on the surface of the conductive substrate;
And oxidizing the surface of the metal manganese or manganese alloy with the porous structure prepared by electroplating in an aerobic environment, and forming manganese oxide or manganese alloy oxide on the surface of the pore wall of the porous structure.
Further, it is:
Manganese salt and ammonium salt are added into the electroplating solution for electroplating.
Salts of alloy elements forming manganese alloy are also added to the plating solution for preparing the manganese alloy catalyst.
The concentration of manganese salt in the electroplating solution is in the range of 0.08-1M, and the concentration of ammonium salt is in the range of 0.15-2M.
The plating solution for electroplating can also be added with 0.001-0.015M of Na2SnO3 or SeO2.
The current density ranges from 100 to 2000mA/cm2.
The electroplating process adopts a mode of rotating the conductive substrate or a mode of stirring the plating solution by adopting a stirring device.
The invention provides a porous structure of a metal manganese and manganese alloy catalyst and a manufacturing method thereof. The method has simple manufacturing process and high production efficiency, and can greatly improve the effective reaction area of the catalyst. In particular, the catalyst is used as an electrode material, can obviously reduce the resistance and improve the electrode performance.
Drawings
FIG. 1 is a schematic view of a rotary electroplating apparatus;
fig. 2 is an SEM photograph of the metal manganese catalyst of the electroplated porous structure. a) A low magnification photograph; b) High magnification photographs;
FIG. 3 is a schematic view of a stirring electroplating device;
FIG. 4 is a stereomicroscope photograph of a metal manganese catalyst with a current density of 1000mA/cm 2 electroplated porous structure with Na 2SnO3 added to the solution;
FIG. 5 is a stereomicroscope photograph of a metal manganese catalyst with a plating porous structure, in which Na 2SnO3 was added to the solution and the current density was 100mA/cm 2;
FIG. 6 is an SEM photograph of an electroplated porous structured metal Mn-Co alloy catalyst with a current density of 1250mA/cm 2 with the addition of SeO 2 to the solution, wherein a), b), c) exhibit porous structures of the catalyst at different magnifications;
FIG. 7 is an SEM photograph of a metal Mn-Co alloy catalyst of electroplated porous structure with a current density of 1500mA/cm 2 with SeO 2 added to the solution, wherein a), b), c) exhibit porous structures of the catalyst at different magnification.
The drawings are marked with the following description:
1. Cathode electrode
2. Anode
3. Plating solution
4. Plating tank
5. Conducting wire
6. Power supply
7. Electrode rotating device
8. Stirring device
Detailed Description
The invention will be further elucidated with reference to a preferred embodiment shown in the drawings.
Embodiment one: the porous structure metal manganese catalyst (figure 1) is electroplated by adopting the rotary electroplating device of figure 1 by taking a metal copper sheet as a cathode 1 and a metal titanium plate as an anode 2. Manganese sulfate is adopted as manganese salt in the plating solution, and the concentration is 0.18M. Ammonium salt in the plating solution adopts ammonium sulfate, and the concentration is 0.9M. 0.001M SeO 2 was added to the plating solution. The pH of the solution was 7.1 and the temperature was 18 ℃.
The dirt, oil and oxide on the surface of the metal copper sheet are removed and then connected with an electrode rotating device 7. A power supply 6 is connected. And starting the electrode rotating device 7, then starting the power supply 6, controlling the current on the surface of the cathode to be 500mA/cm 2, electroplating for 75 seconds, taking out, preparing the porous structure manganese metal catalyst on the surface of the copper sheet (figure 2 a), and viewing the nano-convex structure of the pore wall in figure 2 b. The pore wall is made of manganese oxide nanoparticles in small quantity, and the surface of the pore wall is wrapped with manganese oxide formed in air.
The electrochemical workstation is adopted, a three-electrode test system is adopted in a KOH solution with the concentration of 0.1M at the temperature of 25 ℃, a reference electrode is an Hg/HgO electrode, an auxiliary electrode is a ruthenium-titanium net, a working electrode is a porous structure metal manganese-cobalt alloy catalyst with the apparent area of 1cm 2 prepared by electroplating, a cyclic voltammetry curve is tested in the potential range of 0.926-1.026V, and the capacitance of the porous structure metal manganese-cobalt alloy catalyst prepared by the embodiment is obtained through calculation. Dividing the capacitance value by the capacitance value of the ideal smooth oxide surface to obtain the true surface area of the porous metal manganese-cobalt alloy catalyst prepared by electroplating in the embodiment is 563cm 2.
Embodiment two: and (3) taking a metal manganese sheet as an anode 2, taking the metal copper sheet as a cathode 1, and electroplating the porous structure metal manganese catalyst by adopting the stirring electroplating device shown in fig. 3. Manganese sulfate is adopted as manganese salt in the plating solution, and the concentration is 0.25M. Ammonium chloride is adopted as ammonium salt in the plating solution, and the concentration is 1.2M. 0.001M Na 2SnO3 was added to the plating solution. The pH value of the solution is 6.8 and the temperature is 20 ℃.
The agitation plating apparatus of FIG. 3 was employed. The dirt, oil and oxide on the surface of the metal copper sheet are removed, and then the metal copper sheet is put into an electrolytic tank 4 shown in fig. 3 to be used as a cathode 1, and the metal manganese sheet is used as an anode 2 and is connected with a power supply 6. The stirring device 8 is started to stir the plating solution 3, the power supply 6 is started, the current on the surface of the cathode is controlled to be 1000mA/cm 2, the plating is carried out for 300 seconds, the plating solution is taken out, and the porous structure manganese metal catalyst is prepared on the surface of the copper sheet (figure 4). And (3) placing the metal manganese catalyst with the electroplated porous structure in a heat treatment furnace at 150 ℃ for heating for 30 minutes, and forming a layer of manganese oxide on the surface of the pore wall of the metal manganese with the electroplated porous structure.
Embodiment III: and (3) electroplating the porous structure metal manganese catalyst by using a metal copper sheet as a cathode 1 and a metal manganese sheet as an anode 2 through adopting the stirring electroplating device shown in fig. 3. Manganese chloride is adopted as manganese salt in the plating solution, and the concentration is 0.6M. Ammonium chloride is adopted as ammonium salt in the plating solution, and the concentration is 1.5M. 0.002M SeO 2 was added to the plating solution. The pH of the solution was 7.5 at 22 ℃. The dirt, oil and oxide on the surface of the metal copper sheet are removed and then put into the electrolytic tank 4 of fig. 3 to be connected with a power supply 6. The stirring device 8 is started to stir the plating solution 3, the power supply 6 is started, the current on the surface of the cathode is controlled to be 100mA/cm 2, the plating is carried out for 150 seconds, and then the plating solution is taken out, so that the porous structure manganese metal catalyst is prepared on the surface of the copper sheet (figure 5). The pore wall is made of manganese metal, and the surface of the pore wall is wrapped with a layer of manganese oxide formed in air.
Embodiment four: and (3) electroplating the porous manganese-cobalt alloy catalyst by using a rotary electroplating device shown in fig. 1 by using a metal copper sheet as a cathode 1 and a metal manganese sheet as an anode. Manganese sulfate is adopted as manganese salt in the plating solution, and the concentration is 0.2M. Cobalt salt in the plating solution adopts cobalt sulfate with the concentration of 0.01M. Ammonium salt in the plating solution adopts ammonium sulfate with the concentration of 2M. 0.001M SeO 2 was added to the plating solution. The pH of the solution was 7.0 at 25 ℃.
The dirt, oil and oxide on the surface of the metal copper sheet are removed and then put into the electrolytic tank 4 in fig. 1 to be connected with the electrode rotating device 7 and connected with the power supply 6. After the electrode rotating device 7 was started, the power supply 6 was started, the current on the surface of the cathode was controlled to 1250mA/cm 2, and after 80 seconds of electroplating, the catalyst was taken out, and a porous structure metal Mn-Co alloy catalyst having a cobalt content of 10% wt was prepared on the surface of the copper sheet (FIG. 6). The porous metal Mn-Co alloy catalyst is exposed to air after being taken out from the plating solution, and a layer of Mn-Co alloy oxide is formed on the surface of the pore wall.
The electrochemical workstation is adopted, a three-electrode test system is adopted in a KOH solution with the concentration of 0.1M at the temperature of 25 ℃, a reference electrode is an Hg/HgO electrode, an auxiliary electrode is a ruthenium-titanium net, a working electrode is a porous structure metal manganese-cobalt alloy catalyst with the apparent area of 1cm 2 prepared by electroplating, a cyclic voltammetry curve is tested in the potential range of 0.926-1.026V, and the capacitance of the porous structure metal manganese-cobalt alloy catalyst prepared by the embodiment is obtained through calculation. Dividing the capacitance value by the capacitance value of the ideal smooth oxide surface to obtain the actual surface area of the porous metal Mn-Co alloy catalyst prepared by electroplating in the embodiment is 1305cm 2.
Fifth embodiment: and electroplating the porous manganese-cobalt alloy catalyst by using a metal copper sheet as a cathode 1 and a metal manganese sheet as an anode and adopting the rotary electroplating device shown in fig. 1. Manganese sulfate is adopted as manganese salt in the plating solution, and the concentration is 0.2M. Cobalt salt in the plating solution adopts cobalt sulfate with the concentration of 0.002M. Ammonium salt in the plating solution adopts ammonium sulfate with the concentration of 1.8M. 0.001M SeO 2 was added to the plating solution. The pH of the solution was 7.3 at 25 ℃.
The dirt, oil and oxide on the surface of the metal copper sheet are removed and then put into the electrolytic tank 4 in fig. 1 to be connected with the electrode rotating device 7 and connected with the power supply 6. After the electrode rotating device 7 was started, the power supply 6 was started, the current on the surface of the cathode was controlled to 1500mA/cm 2, and after 80 seconds of electroplating, the catalyst was taken out, and a porous structure metal Mn-Co alloy catalyst having a cobalt content of 2% wt was prepared on the surface of the copper sheet (FIG. 7). A small amount of manganese-cobalt alloy oxide nanoparticles are present in the manganese alloy of the pore wall.
The electrochemical workstation is adopted, a three-electrode test system is adopted in a KOH solution with the concentration of 0.1M at the temperature of 25 ℃, a reference electrode is an Hg/HgO electrode, an auxiliary electrode is a ruthenium-titanium net, a working electrode is a porous structure metal manganese-cobalt alloy catalyst with the apparent area of 1cm 2 prepared by electroplating, a cyclic voltammetry curve is tested in the potential range of 0.926-1.026V, and the capacitance of the porous structure metal manganese-cobalt alloy catalyst prepared by the embodiment is obtained through calculation. Dividing the capacitance value by the capacitance value of the ideal smooth oxide surface to obtain the actual surface area of the porous metal manganese-cobalt alloy catalyst prepared by electroplating in the embodiment is 502cm 2.
In this embodiment, a metal titanium sheet may be used as the cathode 1, and the porous manganese-cobalt alloy catalyst with a cobalt content of 2% wt prepared on the surface of the titanium sheet may be separated from the base titanium sheet by the same electroplating process.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (2)
1. A method for manufacturing a metal manganese or manganese alloy catalyst comprises the following steps:
The plating method is adopted for manufacturing: taking a conductive substrate as a cathode, and taking a metal manganese or manganese alloy or ruthenium-titanium mesh or platinum-plated titanium mesh or titanium mesh as an anode, and placing the anode into an electrolytic tank; the cathode and the anode are respectively connected with the cathode and the anode of the power supply; controlling the current density, and electroplating metal manganese or manganese alloy with a porous structure on the surface of the conductive substrate;
oxidizing the surface of metal manganese or manganese alloy with a porous structure prepared by electroplating in an aerobic environment, and forming manganese oxide or manganese alloy oxide on the surface of the pore wall of the porous structure; the catalyst is of a porous structure, and microprotrusions of a nano structure exist on the surface of the pore wall of the catalyst;
manganese salt and ammonium salt are added into the electroplating solution for preparing the metal manganese catalyst, wherein the concentration of the manganese salt in the electroplating solution is in the range of 0.08-1M, and the concentration of the ammonium salt is in the range of 0.15-2M;
salts of alloy elements forming manganese alloy are also added into the plating solution for preparing the manganese alloy catalyst; 0.001-0.015M of Na 2SnO3 or SeO 2 is also added into the electroplating solution;
The current density ranges from 100 to 2000mA/cm 2.
2. A method for producing a manganese metal or manganese alloy catalyst according to claim 1, characterized by:
the electroplating process adopts a mode of rotating the conductive substrate or a mode of stirring the plating solution by adopting a stirring device.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011361322.0A CN114534738B (en) | 2020-11-27 | 2020-11-27 | Metal manganese or manganese alloy catalyst and manufacturing method thereof |
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| CN202011361322.0A CN114534738B (en) | 2020-11-27 | 2020-11-27 | Metal manganese or manganese alloy catalyst and manufacturing method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991009992A1 (en) * | 1989-12-29 | 1991-07-11 | Nkk Corporation | Process for continuously applying electro-deposited manganese or manganese alloy coating to steel plate |
| CN103227057A (en) * | 2013-03-29 | 2013-07-31 | 中南大学 | Method for producing manganese dioxide electrode of supercapacitor |
| CN103272651A (en) * | 2013-05-27 | 2013-09-04 | 浙江大学 | Preparation method of porous metal supported manganese dioxide catalysts for oxygen production implemented by using hydrogen peroxide |
| CN105624727A (en) * | 2016-04-08 | 2016-06-01 | 吉首大学 | Method for simultaneously producing electrolytic manganese metal and electrolytic manganese dioxide in one electrolysis bath |
| CN107863253A (en) * | 2017-10-16 | 2018-03-30 | 天津工业大学 | A kind of nanoporous nickel-iron-manganese alloys/oxides combination electrode and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991009992A1 (en) * | 1989-12-29 | 1991-07-11 | Nkk Corporation | Process for continuously applying electro-deposited manganese or manganese alloy coating to steel plate |
| CN103227057A (en) * | 2013-03-29 | 2013-07-31 | 中南大学 | Method for producing manganese dioxide electrode of supercapacitor |
| CN103272651A (en) * | 2013-05-27 | 2013-09-04 | 浙江大学 | Preparation method of porous metal supported manganese dioxide catalysts for oxygen production implemented by using hydrogen peroxide |
| CN105624727A (en) * | 2016-04-08 | 2016-06-01 | 吉首大学 | Method for simultaneously producing electrolytic manganese metal and electrolytic manganese dioxide in one electrolysis bath |
| CN107863253A (en) * | 2017-10-16 | 2018-03-30 | 天津工业大学 | A kind of nanoporous nickel-iron-manganese alloys/oxides combination electrode and preparation method thereof |
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