CN115663206B - Preparation method of Fe-Ni-B multi-striation sphere structure catalyst - Google Patents
Preparation method of Fe-Ni-B multi-striation sphere structure catalyst Download PDFInfo
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- CN115663206B CN115663206B CN202211126892.0A CN202211126892A CN115663206B CN 115663206 B CN115663206 B CN 115663206B CN 202211126892 A CN202211126892 A CN 202211126892A CN 115663206 B CN115663206 B CN 115663206B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000009713 electroplating Methods 0.000 claims abstract description 46
- 238000005507 spraying Methods 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000010439 graphite Substances 0.000 claims abstract description 24
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 24
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004327 boric acid Substances 0.000 claims abstract description 18
- 230000008021 deposition Effects 0.000 claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 56
- 238000004070 electrodeposition Methods 0.000 claims description 42
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 29
- 239000010936 titanium Substances 0.000 claims description 28
- 229910052719 titanium Inorganic materials 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 17
- 238000004140 cleaning Methods 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 15
- 239000007921 spray Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000005955 Ferric phosphate Substances 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- 229940032958 ferric phosphate Drugs 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 6
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 70
- 230000000694 effects Effects 0.000 abstract description 3
- 238000003487 electrochemical reaction Methods 0.000 abstract description 3
- 238000002347 injection Methods 0.000 abstract description 2
- 239000007924 injection Substances 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 19
- 230000010355 oscillation Effects 0.000 description 14
- 239000000446 fuel Substances 0.000 description 13
- 238000007747 plating Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 229910021642 ultra pure water Inorganic materials 0.000 description 10
- 239000012498 ultrapure water Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 239000004519 grease Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- -1 transition metal salt Chemical class 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910000531 Co alloy Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses a preparation method of a Fe-Ni-B multi-striated sphere structure catalyst, which comprises the following preparation steps: pretreating the carrier to obtain an initial carrier; performing secondary treatment on the initial carrier to obtain an electroplating carrier; spraying the solution to be plated onto the electroplating carrier through a custom graphite nozzle, and forming a Fe-Ni-B multi-grain structure catalyst on the electroplating carrier; wherein the solution to be plated comprises a transition metal element solution and a boric acid solution. The preparation method provided by the invention is simple and easy to operate, and in the preparation process, the electrochemical activity area is increased through electrochemical reaction, so that the electrochemical performance is improved, and the binding force of the Fe-Ni-B multi-striation sphere structure catalyst is better through two modes of deposition and injection.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to the technical field of catalysts of fuel cells, and particularly relates to a preparation method of a Fe-Ni-B catalyst with a multi-striation sphere structure.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are a new type of device that can directly convert chemical energy into electrical energy. The proton exchange membrane battery has no internal energy consumption of rotating parts, does not undergo combustion, and has high energy conversion efficiency because the energy conversion efficiency is not limited by the Carnot cycle. And the proton exchange membrane battery adopts clean energy, such as hydrogen fuel, has no harm to the environment and has high environmental protection. The proton exchange membrane battery also has the characteristics of mild working condition, small volume, light weight, safety and durability, and is widely used as a mobile power supply, which is also an ideal power supply.
At present, the preparation of hydrogen fuel for proton exchange membrane fuel cells is increasingly receiving attention from various countries. The hydrogen fuel has rich sources, and can prepare hydrogen by utilizing the water electrolysis hydrogen production technology. However, the existing hydrogen fuel preparation catalyst is mainly platinum or platinum cobalt alloy, and the noble metal catalyst has the characteristic of scarcity, so that mass production is difficult to realize, and the preparation of a non-noble metal catalyst is needed.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a Fe-Ni-B multi-striation sphere structure catalyst, and aims to solve the problems that the existing fuel cell catalyst is prepared by noble metals, the cost is high and mass production is difficult to realize.
In order to achieve the above purpose, the preparation method of the Fe-Ni-B multi-striated sphere structure catalyst provided by the invention comprises the following preparation steps:
pretreating the carrier to obtain an initial carrier;
performing secondary treatment on the initial carrier to obtain an electroplating carrier;
spraying the solution to be plated onto the electroplating carrier through a customized graphite nozzle, and forming an Fe-Ni-B multi-grain structure catalyst on the electroplating carrier;
wherein the solution to be plated comprises a transition metal element solution and a boric acid solution.
Optionally, the transition metal solution includes a metal solution of Fe element and a metal solution of Ni element, wherein:
the metal solution of the Fe element comprises at least one of ferric chloride, ferric sulfate and ferric phosphate;
the metal solution of Ni element comprises at least one of nickel chloride, nickel sulfate and ferric phosphate.
Optionally, in the solution to be plated, the concentration of the boric acid solution is 0.5-1.5 mol/L.
Optionally, in the solution to be plated, the concentration ratio of the transition metal salt to the boric acid is (1.58-4): 1.
optionally, the step of depositing and spraying the solution to be plated onto the electroplating carrier through a custom graphite nozzle, and forming the Fe-Ni-B multi-striated sphere structure catalyst on the electroplating carrier comprises the following steps:
and taking the electroplating carrier as a cathode, taking a customized graphite nozzle as an anode, and sequentially spraying the to-be-plated liquid on the electroplating carrier by using an electrodeposition mode to spray the electrodeposition mode through the customized graphite nozzle so as to form the Fe-Ni-B multi-striation structure catalyst.
Optionally, in the electrodeposition mode: the deposition current is 0.15-0.6A, the deposition temperature is 30-80 ℃, and the deposition time is 10-15 s.
Optionally, in the spray electrodeposition mode: the deposition voltage is 1-6V, the deposition time is 3-15 s, the deposition temperature is 30-80 ℃, the spraying amount of the to-be-plated liquid is 0.2-1 mL/s, and the distance between the nozzle and the electroplating carrier is 2-10 mm.
Optionally, the step of pre-treating the carrier to obtain an initial carrier comprises: immersing the carrier into sulfuric acid solution with the concentration of 0.1-0.8 mol/L, carrying out ultrasonic oscillation treatment for 1-10 min, taking out, immersing into deionized water again, carrying out ultrasonic oscillation for 5-10 min, taking out and cleaning to obtain the initial carrier.
Optionally, the step of performing secondary treatment on the initial carrier to obtain an electroplated carrier comprises the following steps: immersing the initial carrier in sulfuric acid with the concentration of 0.2-0.8 mol/L at the temperature of 30-90 ℃, heating for 2-8 min, taking out, immersing in sulfuric acid with the concentration of 1-2 mol/L, conducting electrifying treatment for 3-5 min, taking out and cleaning to obtain the electroplating carrier.
Optionally, the carrier is a titanium plate.
In the technical scheme of the invention, the carrier is preprocessed to obtain an initial carrier; performing secondary treatment on the initial carrier to obtain an electroplating carrier; spraying the solution to be plated onto the electroplating carrier through a customized graphite nozzle, and forming an Fe-Ni-B multi-grain structure catalyst on the electroplating carrier; the preparation method provided by the invention is simple and easy to operate, and in the preparation process, the electrochemical activity area is increased through electrochemical reaction, so that the electrochemical performance is improved, and the binding force of the Fe-Ni-B multi-striation sphere structure catalyst is better through two modes of deposition and injection.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a Fe-Ni-B multi-striated sphere catalyst provided by the invention;
FIG. 2 is a schematic flow chart of an embodiment of a method for preparing a Fe-Ni-B multi-striated sphere catalyst according to the present invention;
FIG. 3 is a graph showing the performance of the Fe-Ni-B multi-striated sphere catalyst prepared in example 1 of the present invention in hydrogen evolution test;
FIG. 4 is a graph showing the performance of the Fe-Ni-B multi-striated sphere catalyst prepared in example 2 of the present invention in hydrogen evolution test;
FIG. 5 is a graph showing the performance of the Fe-Ni-B multi-striated sphere catalyst prepared in example 3 of the present invention in hydrogen evolution test;
FIG. 6 is a graph showing the performance of the Fe-Ni-B multi-striated sphere catalyst prepared in example 4 of the present invention in hydrogen evolution test;
FIG. 7 is a graph showing the performance of the Fe-Ni-B multi-striated sphere catalyst prepared in example 5 of the present invention in hydrogen evolution test.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. In addition, the meaning of "and/or" as it appears throughout includes three parallel schemes, for example "A and/or B", including the A scheme, or the B scheme, or the scheme where A and B are satisfied simultaneously. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be regarded as not exist and not within the protection scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
At present, the preparation of hydrogen fuel for proton exchange membrane fuel cells is increasingly receiving attention from various countries. The hydrogen fuel has rich sources, and can prepare hydrogen by utilizing the water electrolysis hydrogen production technology. However, the existing hydrogen fuel preparation catalyst is mainly platinum or platinum cobalt alloy, and the noble metal catalyst has the characteristic of scarcity, so that mass production is difficult to realize, and the preparation of a non-noble metal catalyst is needed.
In view of the above, the invention provides a preparation method of the Fe-Ni-B multi-striated sphere structure catalyst, and the Fe-Ni-B multi-striated sphere structure catalyst prepared by the preparation method has better electrochemical performance, stronger binding force and longer service life; referring to fig. 2, a flow chart of an embodiment of a method for preparing a catalyst with a multi-striated ball structure of Fe-Ni-B according to the present invention includes the following steps:
step S10, preprocessing the carrier to obtain an initial carrier.
In this embodiment, the material of the carrier is not limited as long as the carrier can achieve electrical conduction, and specifically, the carrier is a titanium plate.
In the step S10, the following steps may be specifically performed: immersing the carrier in sulfuric acid solution with the concentration of 0.1-0.8 mol/L, carrying out ultrasonic oscillation treatment for 1-10 min, taking out, immersing in deionized water again, carrying out ultrasonic oscillation for 5-10 min, taking out and cleaning to obtain an initial carrier; in this embodiment, the purpose of adding the sulfuric acid solution is to remove the oxide impurities on the surface of the carrier by reacting the sulfuric acid solution with the oxide substances on the surface of the carrier.
And step S20, performing secondary treatment on the initial carrier to obtain an electroplating carrier.
In the step S20, the following steps may be specifically performed: immersing the initial carrier in sulfuric acid with the concentration of 0.2-0.8 mol/L at the temperature of 30-90 ℃, heating for 2-8 min, taking out, immersing in sulfuric acid with the concentration of 1-2 mol/L, conducting electrifying treatment for 3-5 min, taking out and cleaning to obtain the electroplating carrier; further, in this embodiment, some substances such as grease impurities may exist on the surface of the initial carrier, and by immersing the initial carrier in the sulfuric acid solution, the grease impurities and the like on the surface of the initial carrier react with the sulfuric acid solution, so as to remove the grease impurities and the like on the surface of the initial carrier, and avoid the grease impurities and the like from being adsorbed on the surface of the initial carrier, which affects spraying in a subsequent step; meanwhile, the purpose of the electrifying treatment is to carry out anodic oxidation treatment on the initial carrier so as to increase the surface cleanliness of the initial carrier.
S30, spraying the to-be-plated liquid onto the electroplating carrier through a customized graphite nozzle, and forming an Fe-Ni-B multi-striation structure catalyst on the electroplating carrier;
wherein the solution to be plated comprises a transition metal element solution and a boric acid solution.
The noble metal is mainly a metal compound containing 8 elements of ruthenium element, rhodium element, palladium element, osmium element, iridium element, and platinum element; and the non-noble metal means a metal element compound other than gold element, silver element, ruthenium element, rhodium element, palladium element, osmium element, iridium element, and platinum element; generally, the non-noble metal elements include iron element, aluminum element, manganese element, nickel element, titanium element, copper element, and the like, and therefore, in the present embodiment, a compound containing iron element and nickel element is selected as the solution to be plated in consideration of manufacturing cost and process requirements.
Specifically, in some embodiments, the transition metal solution is preferably a metal solution of Fe element and a metal solution of Ni element, more specifically, the metal solution of Fe element includes ferric chloride, in view of stability and catalytic activity of the finally prepared fe—ni-B multi-striated catalyst; the metal solution of Ni element comprises nickel chloride. As a preferred embodiment of the present embodiment, the transition metal solution includes ferric chloride and nickel chloride.
Further, in some embodiments, the concentration of the boric acid solution in the solution to be plated is 0.5 to 1.5mol/L, specifically, the concentration of the boric acid solution may be 0.5mol/L, may be 0.8mol/L, may be 1.0mol/L, may be 1.2mol/L, and may be 1.5mol/L; the specific situation can be selected according to the actual requirement; the boric acid solution serves to alleviate localized alkaline of the plating.
Further, in order to improve the catalytic activity and stability of the prepared Fe-Ni-B multi-striated sphere structure catalyst, in the implementation, the concentration ratio of the transition metal salt to the boric acid in the solution to be plated is (1.5-4): 1, a step of; if the amount exceeds the above range, it is difficult to alleviate the local alkalization effect; as a preferred embodiment of the present embodiment, the concentration ratio of the transition metal salt to the boric acid is 1.5:1.
in performing step S30, it may be performed by: and spraying the to-be-plated liquid onto the electroplating carrier by using an electrodeposition mode and a spraying electrodeposition mode through the customized graphite nozzle by using the electroplating carrier as a cathode and using the customized graphite nozzle as an anode so as to form the Fe-Ni-B multi-striation structure catalyst.
In this embodiment, the Fe-Ni-B multi-striation catalyst is prepared by electrodeposition and spray electrodeposition, so that the defect of local change of the concentration of the solution existing in static electrodeposition can be effectively prevented, and the binding force of the catalyst is better.
In particular, in practice, it is also necessary to pay attention to the conditions of the electrodeposition, in some embodiments, the current of the electrodeposition regime is between 0.15 and 0.6A, the temperature of the electrodeposition regime is between 30 and 80 ℃, and the time of the electrodeposition regime is between 10 and 15 seconds.
In some embodiments, the voltage of the spray electrodeposition mode is 1-6V, the time of the spray electrodeposition mode is 3-15 s, the temperature of the spray electrodeposition mode is 30-80 ℃, and the spray amount of the spray electrodeposition mode is 0.2-1 mL/s.
Further, in the spray electrodeposition mode, the distance from the nozzle to the plating carrier is 2 to 10mm. In the distance range, the to-be-plated liquid can be ensured to be uniformly sprayed on the electroplating carrier, and the binding force of the catalyst is ensured.
The custom graphite nozzle has a conical structure, and the diameter of the nozzle is 5mm.
The following technical solutions of the present invention will be described in further detail with reference to specific examples and drawings, and it should be understood that the following examples are only for explaining the present invention and are not intended to limit the present invention.
Example 1
(1) Selecting a titanium plate with the size of 2cm multiplied by 2cm as a carrier to prepare a catalyst;
(2) Immersing the titanium plate in sulfuric acid solution with the concentration of 0.1mol/L, carrying out ultrasonic oscillation treatment for 8min, taking out, cleaning with ultrapure water, immersing in ultrapure water, carrying out oscillation treatment for 5min, and taking out to obtain an initial titanium plate;
(3) Immersing an initial titanium plate in sulfuric acid with the concentration of 0.2mol/L at the temperature of 30 ℃, heating for 8min, taking out, immersing in sulfuric acid with the concentration of 1mol/L, electrifying for 5min, taking out and cleaning to obtain an electroplated titanium plate;
(4) 40mL of a solution to be plated is obtained, wherein the solution contains 0.2mol/L anhydrous ferric chloride, 0.3mol/L nickel chloride and 0.5mol/L boric acid;
(5) Taking an electroplating carrier as a cathode, taking a customized graphite nozzle as an anode, and spraying the to-be-plated liquid onto the electroplating carrier through the customized graphite nozzle in an electrodeposition mode and a spray electrodeposition mode to form an Fe-Ni-B multi-striation structure catalyst; wherein:
the electrodeposition process parameters are: the current is 0.15A, the temperature is 30 ℃, and the time is 10s;
the jet electrodeposition process parameters were: the electroplating time is 3s, the power supply voltage is 1V, the spraying amount of the plating solution is 0.2mL/s, the distance between the nozzle and the carrier is 2mm, and the temperature of the mixed plating solution is 30 ℃.
Example 2
(1) Selecting a titanium plate with the size of 2cm multiplied by 2cm as a carrier to prepare a catalyst;
(2) Immersing the titanium plate in sulfuric acid solution with the concentration of 0.1mol/L, carrying out ultrasonic oscillation treatment for 8min, taking out, cleaning with ultrapure water, immersing in ultrapure water, carrying out oscillation treatment for 5min, and taking out to obtain an initial titanium plate;
(3) Immersing an initial titanium plate in sulfuric acid with the concentration of 0.2mol/L at the temperature of 30 ℃, heating for 8min, taking out, immersing in sulfuric acid with the concentration of 1mol/L, electrifying for 5min, taking out and cleaning to obtain an electroplated titanium plate;
(4) 40mL of to-be-plated liquid containing 1mol/L anhydrous ferric phosphate, 1mol/L nickel sulfate and 1mol/L boric acid is obtained;
(5) Taking an electroplating carrier as a cathode, taking a customized graphite nozzle as an anode, and spraying the to-be-plated liquid onto the electroplating carrier through the customized graphite nozzle in an electrodeposition mode and a spray electrodeposition mode to form an Fe-Ni-B multi-striation structure catalyst; wherein:
the electrodeposition process parameters are: the current is 0.4A, the temperature is 50 ℃ and the time is 12s;
the jet electrodeposition process parameters were: the electroplating time is 10s, the power supply voltage is 4V, the spraying amount of the plating solution is 0.5mL/s, the distance between the nozzle and the carrier is 5mm, and the temperature of the mixed plating solution is 50 ℃.
Example 3
(1) Selecting a titanium plate with the size of 2cm multiplied by 2cm as a carrier to prepare a catalyst;
(2) Immersing the titanium plate in sulfuric acid solution with the concentration of 0.5mol/L, carrying out ultrasonic oscillation treatment for 6min, taking out, cleaning by using ultrapure water, immersing in ultrapure water, carrying out oscillation treatment for 4min, and taking out to obtain an initial titanium plate;
(3) Immersing an initial titanium plate in sulfuric acid with the concentration of 0.6mol/L at 50 ℃, heating for 5min, taking out, immersing in sulfuric acid with the concentration of 1mol/L, electrifying for 5min, taking out and cleaning to obtain an electroplated titanium plate;
(4) 40mL of a solution to be plated containing 1.2mol/L anhydrous sulfated iron, 1.1mol/L nickel chloride and 1.1mol/L boric acid was obtained;
(5) Taking an electroplating carrier as a cathode, taking a customized graphite nozzle as an anode, and spraying the to-be-plated liquid onto the electroplating carrier through the customized graphite nozzle in an electrodeposition mode and a spray electrodeposition mode to form an Fe-Ni-B multi-striation structure catalyst; wherein:
the electrodeposition process parameters are: the current is 0.5A, the temperature is 60 ℃, and the time is 13s;
the jet electrodeposition process parameters were: the electroplating time is 11s, the power supply voltage is 5V, the spraying amount of the plating solution is 0.6mL/s, the distance between the nozzle and the carrier is 7mm, and the temperature of the mixed plating solution is 60 ℃.
Example 4
(1) Selecting a titanium plate with the size of 2cm multiplied by 2cm as a carrier to prepare a catalyst;
(2) Immersing the titanium plate in sulfuric acid solution with the concentration of 0.2mol/L, carrying out ultrasonic oscillation treatment for 10min, taking out, cleaning with ultrapure water, immersing in ultrapure water, carrying out oscillation treatment for 5min, and taking out to obtain an initial titanium plate;
(3) Immersing an initial titanium plate in sulfuric acid with the concentration of 0.8mol/L at the temperature of 40 ℃, heating for 5min, taking out, immersing in sulfuric acid with the concentration of 1.5mol/L, electrifying for 4min, taking out and cleaning to obtain an electroplated titanium plate;
(4) 40mL of a solution to be transited is obtained, wherein the solution contains 1.4mol/L anhydrous ferric chloride, 1.2mol/L nickel sulfate and 1.3mol/L boric acid;
(5) Taking an electroplating carrier as a cathode, taking a customized graphite nozzle as an anode, and spraying the to-be-plated liquid onto the electroplating carrier through the customized graphite nozzle in an electrodeposition mode and a spray electrodeposition mode to form an Fe-Ni-B multi-striation structure catalyst; wherein:
the electrodeposition process parameters are: the current is 0.6A, the temperature is 70 ℃ and the time is 14s;
the jet electrodeposition process parameters were: the electroplating time is 13s, the power supply voltage is 6V, the spraying amount of the plating solution is 0.7mL/s, the distance between the nozzle and the carrier is 9mm, and the temperature of the mixed plating solution is 70 ℃.
Example 5
(1) Selecting a titanium plate with the size of 2cm multiplied by 2cm as a carrier to prepare a catalyst;
(2) Immersing the titanium plate in sulfuric acid solution with the concentration of 0.8mol/L, carrying out ultrasonic oscillation treatment for 1min, taking out, cleaning with ultrapure water, immersing in ultrapure water, carrying out oscillation treatment for 5min, and taking out to obtain an initial titanium plate;
(3) Immersing an initial titanium plate in sulfuric acid with the concentration of 0.8mol/L at 90 ℃, heating for 2min, taking out, immersing in sulfuric acid with the concentration of 2mol/L, electrifying for 5min, taking out and cleaning to obtain an electroplated titanium plate;
(4) 50mL of a solution to be plated is obtained, wherein the solution contains 2mol/L of anhydrous ferric phosphate, 1.5mol/L of nickel phosphate and 1.5mol/L of boric acid;
(5) Taking an electroplating carrier as a cathode, taking a customized graphite nozzle as an anode, and spraying the to-be-plated liquid onto the electroplating carrier through the customized graphite nozzle in an electrodeposition mode and a spray electrodeposition mode to form an Fe-Ni-B multi-striation structure catalyst; wherein:
the electrodeposition process parameters are: the current is 0.6A, the temperature is 80 ℃ and the time is 15s;
the jet electrodeposition process parameters were: the electroplating time is 15s, the power supply voltage is 6V, the spraying amount of the plating solution is 1mL/s, the distance between the nozzle and the carrier is 10mm, and the temperature of the mixed plating solution is 80 ℃.
Comparative example 1
Commercial catalyst, model number (HiCaP 40).
Performance testing
(1) Specific surface area detection
The specific surface area of the Fe-Ni-B multi-striated sphere structured catalysts prepared in examples 1 to 5 and comparative example 1 was measured, and the specific test data are shown in Table 1.
TABLE 1 specific surface area
As can be seen from fig. 1 and table 1, the Fe-Ni-B multi-striated sphere structured catalysts prepared in examples 1 to 5 have a larger specific surface area, can expose a larger area, and can increase an electrochemically active area during electrochemical reaction, thereby improving electrochemical performance.
(2) Hydrogen evolution test Performance test
The Fe-Ni-B multi-striated sphere structured catalysts prepared in examples 1 to 5 and comparative example 1 were tested for hydrogen evolution performance, and the test results are shown in FIGS. 3 to 7.
From fig. 3, 4, 5, 6 and 7, it can be seen that the hydrogen evolution performance is gradually improved as the concentration increases.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the scope of the present invention, but various modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (4)
1. The preparation method of the Fe-Ni-B multi-striated sphere structure catalyst is characterized by comprising the following preparation steps:
pretreating the carrier to obtain an initial carrier;
performing secondary treatment on the initial carrier to obtain an electroplating carrier;
spraying the solution to be plated onto the electroplating carrier through a customized graphite nozzle, and forming an Fe-Ni-B multi-grain structure catalyst on the electroplating carrier;
wherein the solution to be plated comprises a transition metal element solution and a boric acid solution, the transition metal element solution comprises a metal solution of Fe element and a metal solution of Ni element, wherein:
the metal solution of the Fe element comprises at least one of ferric chloride, ferric sulfate and ferric phosphate; the metal solution of the Ni element comprises at least one of nickel chloride, nickel sulfate and ferric phosphate;
in the solution to be plated, the concentration of the boric acid solution is 0.5-1.5 mol/L; the concentration ratio of the transition metal element solution to the boric acid solution is (1.58-4): 1, a step of;
the method comprises the steps of depositing and spraying a solution to be plated on the electroplating carrier through a customized graphite nozzle, and forming an Fe-Ni-B multi-grain structure catalyst on the electroplating carrier, wherein the steps comprise:
taking the electroplating carrier as a cathode, taking a customized graphite nozzle as an anode, and sequentially spraying a to-be-plated liquid onto the electroplating carrier by using an electrodeposition mode and a spraying electrodeposition mode through the customized graphite nozzle to form an Fe-Ni-B multi-grain sphere structure catalyst;
in the electrodeposition mode: the deposition current is 0.15-0.6A, the deposition temperature is 30-80 ℃, and the deposition time is 10-15 s;
in the spray electrodeposition mode: the deposition voltage is 1-6V, the deposition time is 3-15 s, the deposition temperature is 30-80 ℃, the spraying amount of the to-be-plated liquid is 0.2-1 mL/s, and the distance between the nozzle and the electroplating carrier is 2-10 mm.
2. The method for preparing a Fe-Ni-B multi-striated sphere structured catalyst according to claim 1, wherein the step of pre-treating the support to obtain an initial support comprises: immersing the carrier in sulfuric acid solution with the concentration of 0.1-0.8 mol/L, carrying out ultrasonic vibration treatment for 1-10 min, taking out, immersing in deionized water again, carrying out ultrasonic vibration for 5-10 min, taking out and cleaning to obtain the initial carrier.
3. The method for preparing the Fe-Ni-B multi-striated sphere structure catalyst according to claim 1, wherein the step of performing secondary treatment on the initial carrier to obtain an electroplated carrier comprises: and immersing the initial carrier in sulfuric acid with the concentration of 0.2-0.8 mol/L at the temperature of 30-90 ℃, heating for 2-8 min, taking out, immersing in sulfuric acid with the concentration of 1-2 mol/L, carrying out power-on treatment for 3-5 min, taking out and cleaning to obtain the electroplating carrier.
4. The method for preparing a catalyst having a multi-striated ball structure of Fe-Ni-B according to claim 1, wherein the carrier is a titanium plate.
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| JPH08148142A (en) * | 1994-11-25 | 1996-06-07 | Katayama Tokushu Kogyo Kk | Manufacture of metal porous body for battery electrode plate and metal porous body for battery electrode plate |
| CN101509140A (en) * | 2009-02-13 | 2009-08-19 | 燕山大学 | Process for spray electrodeposition Ni-Fe alloy coating on surface of copper or copper alloy |
| JP2021085048A (en) * | 2019-11-26 | 2021-06-03 | Ｊｆｅスチール株式会社 | METHOD OF PRODUCING STEEL SHEET PLATED WITH Zn-Ni BASED ALLOY, AND ELECTROPLATING FACILITY |
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| CN114984961A (en) * | 2022-06-02 | 2022-09-02 | 江苏师范大学 | Ternary alloy catalyst Fe-Co-Ni for hydrogen production by hydrolysis of borohydride and preparation method thereof |
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| JPH08148142A (en) * | 1994-11-25 | 1996-06-07 | Katayama Tokushu Kogyo Kk | Manufacture of metal porous body for battery electrode plate and metal porous body for battery electrode plate |
| CN101509140A (en) * | 2009-02-13 | 2009-08-19 | 燕山大学 | Process for spray electrodeposition Ni-Fe alloy coating on surface of copper or copper alloy |
| JP2021085048A (en) * | 2019-11-26 | 2021-06-03 | Ｊｆｅスチール株式会社 | METHOD OF PRODUCING STEEL SHEET PLATED WITH Zn-Ni BASED ALLOY, AND ELECTROPLATING FACILITY |
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