CN114808007A - Method for preparing Ni-Fe-Cu-Co-W high-entropy alloy electrocatalyst by electrodeposition method - Google Patents
Method for preparing Ni-Fe-Cu-Co-W high-entropy alloy electrocatalyst by electrodeposition method Download PDFInfo
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- 238000004070 electrodeposition Methods 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 24
- 229910020515 Co—W Inorganic materials 0.000 title claims abstract description 23
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 21
- 239000000956 alloy Substances 0.000 title claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 99
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 59
- 239000010439 graphite Substances 0.000 claims abstract description 59
- 239000010935 stainless steel Substances 0.000 claims abstract description 59
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 59
- 229910052742 iron Inorganic materials 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011734 sodium Substances 0.000 claims abstract description 32
- 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 claims abstract description 30
- 239000001509 sodium citrate Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 230000004913 activation Effects 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 56
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 150000002505 iron Chemical class 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 238000005498 polishing Methods 0.000 claims description 10
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 10
- 230000003213 activating effect Effects 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000002344 surface layer Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 238000007747 plating Methods 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910020637 Co-Cu Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/089—Alloys
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
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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
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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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
Abstract
The invention provides a method for preparing a Ni-Fe-Cu-Co-W high-entropy alloy electrocatalyst by an electrodeposition method, which is characterized by comprising the following steps of: the base material is a metallic iron sheet or stainless steel or graphite subjected to activation pretreatment, and the electrodeposition solution has a composition of 6-75 g.L ‑1 FeSO 4 ·7H 2 O,110~250g·L ‑1 Ni 2 SO 4 ·6H 2 O,10~90g·L ‑ 1 NiCl 2 ·6H 2 O,15~150g·L ‑1 CuSO 4 ·5H 2 O,15~150g·L ‑1 CoSO 4 ·7H 2 O,5~100g·L ‑1 Na 2 WO 4 ·2H 2 O,2~50g·L ‑1 H 3 BO 3 ,5~40g·L ‑1 Na 3 PO 4 ·12H 2 O,10~300g·L ‑1 And (3) sodium citrate. Using ammonia water or 2-40 Vol% H 2 SO 4 Adjusting the pH value of the electrodeposition solution to 5-7, and the electrodeposition current density is 5-350 mA-cm ‑2 And the temperature of the plating solution is 5-35 ℃, the electrodeposition time is 0.5-4.5 h, and a Ni-Fe-Cu-Co-W high-entropy alloy deposition layer is obtained. The electrolytic water catalytic electrode has the characteristics of stable performance, low cost, convenient operation and small environmental hazard, is a preparation method of an electrocatalyst with a very promising prospect, and provides a new idea for the development of an electrocatalytic material.
Description
Technical Field
The invention relates to a method for preparing a Ni-Fe-Cu-Co-W high-entropy alloy electrocatalyst by an electrodeposition method, belonging to the technical field of new energy, new materials and hydrogen production by water electrolysis.
Background
With the continuous increase of energy demand, the problems of environmental pollution, greenhouse effect, energy exhaustion and the like caused by traditional fossil energy such as petroleum, coal and the like become serious day by day, and renewable, pollution-free, efficient and economical new energy has become the main direction of current energy research. At the present stage, the most promising energy source with environmental protection and cleanness is hydrogen energy, and the primary choice is to obtain clean hydrogen energy by electrocatalysis water decomposition. In the process of electrolyzing water, two reactions, cathodic Hydrogen Evolution (HER) and anodic Oxygen Evolution (OER), are involved. Compared with the two-electron transfer process of HER, OER is a complex four-electron transfer process and needs higher overpotential, which is a bottleneck limiting the development of water electrolysis hydrogen production technology. IrO 2 、Rb 2 Noble metal oxides such as O and the like have high oxygen evolution catalytic activity, but the popularization and the application of the noble metal oxides are restricted due to high cost and scarce resources.
The high-entropy alloy can keep thermodynamic and kinetic stability of the catalyst due to the unique 'core effect', namely the electronic structure of an active site is optimized by lattice distortion, and the high-entropy effect and the delayed diffusion effect, so that the high-entropy alloy has better catalytic performance than a single-component catalyst; secondly, most of the high-entropy alloys contain transition group metals (Fe, Ni, Co and the like) with low hydrogen evolution overpotential and corrosion-resistant metals (Cu, Al and the like), so that the high-entropy alloys have the advantages of easily available raw materials and corrosion resistance, and show great potential development force in the field of electrochemical catalysis application.
At present, people successfully prepare high-entropy alloy with excellent electrocatalytic activity by methods such as carbon thermal impact, dealloying, mechanical alloying and the like, and researches on preparing the high-entropy alloy by an electrodeposition method are rarely reported and do not have a mature electrodeposition formula. The method creatively adopts an electrodeposition method to prepare the Ni-Fe-W-Co-Cu high-entropy alloy, selectively mixes specific elements in a specific proportion, reduces the content of noble metals, optimizes the electronic structure of active sites, and obtains the catalyst of OER electrocatalytic reaction with excellent performance. The method has low cost, stable performance and convenient operation, is a preparation method of the electrocatalyst with a promising prospect, and provides a new idea for the development of the electrocatalytic material.
Disclosure of Invention
The invention aims to provide a method for preparing a Ni-Fe-Cu-Co-W high-entropy alloy electrocatalyst by an electrodeposition method, which is used for solving the problems in the prior art and obtaining a high-efficiency and stable alkaline oxygen evolution catalyst. The electrolytic water catalytic electrode has the characteristics of stable performance, low cost and convenient operation, is a preparation method of an electrocatalyst with a very promising prospect, and provides a new idea for the development of an electrocatalytic material.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a Ni-Fe-Cu-Co-W high-entropy alloy electrocatalyst by an electrodeposition method comprises the following steps:
(1) polishing a base material by using 800# to 2000# abrasive paper on a metal iron sheet or stainless steel or graphite with the thickness of 0.08 to 20mm, and removing macroscopic flaws such as oxide skin, scratches and the like on the surface layer of the base material;
(2) activating the polished iron sheet, stainless steel or graphite in 5-50 Vol% HCl for 5-100 s at room temperature;
(3) repeatedly washing the activated iron sheet, stainless steel or graphite with deionized water for many times until the pH value is 7 and neutral;
(4) carrying out oil removal treatment on iron sheets, stainless steel or graphite by using acetone, cleaning by using deionized water and then drying;
(5) the electrodeposition liquid has a composition of 6 to 75 g.L -1 FeSO 4 ·7H 2 O,110~250g·L -1 Ni 2 SO 4 ·6H 2 O,10~90g·L -1 NiCl 2 ·6H 2 O,15~150g·L -1 CuSO 4 ·5H 2 O,15~150g·L -1 CoSO 4 ·7H 2 O,5~100g·L - 1 Na 2 WO 4 ·2H 2 O,2~50g·L -1 H 3 BO 3 ,5~40g·L -1 Na 3 PO 4 ·12H 2 O,10~300g·L -1 And (3) sodium citrate. Using ammonia water or 2-40 Vol% H 2 SO 4 Adjusting the pH value of the electrodeposition solution to 5-7;
(6) dissolving NiCl 2 ·6H 2 O、Ni 2 SO 4 ·6H 2 Mixing the O solution and the sodium citrate solution, stirring uniformly, and adding H 3 BO 3 Solution and Na 2 WO 4 Adjusting the pH value of the mixed solution to 5-7, adding sodium citrate, uniformly mixing, and continuously adding FeSO 4 Adjusting the pH value to 5-7, and finally sequentially adding CuSO 4 ·5H 2 O and CoSO 4 ·7H 2 O solution, and adjusting the pH value of the electrodeposition solution to 5-7;
(7) immersing the deoiled iron sheet or stainless steel or graphite into the electrodeposition liquid, taking the iron sheet or stainless steel or graphite as a cathode and a platinum sheet electrode as an anode, and carrying out the electrodeposition at a temperature of 5-25 ℃ and a current density of 5-350 mA-cm -2 Under the condition, carrying out electrodeposition for 0.5-4.5 h;
(8) and after the electrodeposition is finished, taking out the sample, washing the sample by using deionized water, performing ultrasonic cleaning, and drying to obtain the Ni-Fe-Cu-Co-W electrocatalyst.
The invention adopts an electrodeposition method to prepare the Ni-Fe-Cu-Co-W high-entropy alloy catalyst, and compared with the prior art, the invention has the advantages of excellent catalytic performance, simple and easy method, small environmental hazard and the like.
Detailed Description
The present invention will be further clearly understood from the specific examples given below, but the following examples are not intended to limit the present invention.
Example 1:
(1) polishing a base material by using 800# to 2000# abrasive paper on a metal iron sheet or stainless steel or graphite with the thickness of 0.08 to 20mm, and activating the polished iron sheet or stainless steel or graphite in 5 to 50 Vol% HCl for 5 to 100 seconds at room temperature; repeatedly washing the activated iron sheet, stainless steel or graphite with deionized water for many times until the pH value is 7 and neutral; carrying out oil removal treatment on iron sheets, stainless steel or graphite by using acetone, cleaning by using deionized water and then drying;
(2) the electrodeposition liquid has a composition of 6 to 75 g.L -1 FeSO 4 ·7H 2 O,110~250g·L -1 Ni 2 SO 4 ·6H 2 O,10~90g·L -1 NiCl 2 ·6H 2 O,15~150g·L -1 CuSO 4 ·5H 2 O,15~150g·L -1 CoSO 4 ·7H 2 O,5~100g·L - 1 Na 2 WO 4 ·2H 2 O,2~50g·L -1 H 3 BO 3 ,5~40g·L -1 Na 3 PO 4 ·12H 2 O,10~300g·L -1 And (3) sodium citrate. Using ammonia water or 2-40 Vol% H 2 SO 4 Adjusting the pH value of the electrodeposition solution to 5-7;
(3) dissolving NiCl 2 ·6H 2 O、Ni 2 SO 4 ·6H 2 Mixing the O solution and the sodium citrate solution, stirring uniformly, and adding H 3 BO 3 Solution and Na 2 WO 4 Adjusting the pH value of the mixed solution to 5-7, adding sodium citrate, uniformly mixing, and continuously adding FeSO 4 Adjusting the pH value to 5-7, and finally sequentially adding CuSO 4 ·5H 2 O and CoSO 4 ·7H 2 O solutionAdjusting the pH value of the electrodeposition solution to 5-7;
(4) immersing the deoiled iron sheet or stainless steel or graphite into the electrodeposition liquid, taking the iron sheet or the stainless steel or the graphite as a cathode and a platinum sheet electrode as an anode, and carrying out the electrodeposition at the temperature of 10 ℃ and the current density of 5-350 mA-cm -2 Under the condition, carrying out electrodeposition for 0.5-4.5 h;
(5) and after the electrodeposition is finished, taking out the sample, washing the sample by using deionized water, performing ultrasonic cleaning, and drying to obtain the Ni-Fe-Cu-Co-W electrocatalyst.
Example 2:
(1) polishing a base material by using 800# to 2000# abrasive paper on a metal iron sheet or stainless steel or graphite with the thickness of 0.08 to 20mm, and activating the polished iron sheet or stainless steel or graphite in 5 to 50 Vol% HCl for 5 to 100 seconds at room temperature; repeatedly washing the activated iron sheet, stainless steel or graphite with deionized water for many times until the pH value is 7 and neutral; carrying out oil removal treatment on iron sheets, stainless steel or graphite by using acetone, cleaning by using deionized water and then drying;
(2) the electrodeposition liquid has a composition of 6 to 75 g.L -1 FeSO 4 ·7H 2 O,110~250g·L -1 Ni 2 SO 4 ·6H 2 O,10~90g·L -1 NiCl 2 ·6H 2 O,15~150g·L -1 CuSO 4 ·5H 2 O,15~150g·L -1 CoSO 4 ·7H 2 O,5~100g·L - 1 Na 2 WO 4 ·2H 2 O,2~50g·L -1 H 3 BO 3 ,5~40g·L -1 Na 3 PO 4 ·12H 2 O,10~300g·L -1 And (3) sodium citrate. Using ammonia water or 2-40 Vol% H 2 SO 4 Adjusting the pH value of the electrodeposition solution to 5-7;
(3) dissolving NiCl 2 ·6H 2 O、Ni 2 SO 4 ·6H 2 Mixing the O solution and the sodium citrate solution, stirring uniformly, and adding H 3 BO 3 Solution and Na 2 WO 4 Adjusting the pH value of the mixed solution to 5-7, adding sodium citrate, uniformly mixing, and continuously adding FeSO 4 And adjusting the pH value to5-7, and finally sequentially adding CuSO 4 ·5H 2 O and CoSO 4 ·7H 2 O solution, and adjusting the pH value of the electrodeposition solution to 5-7;
(4) immersing the deoiled iron sheet or stainless steel or graphite into the electrodeposition liquid, taking the iron sheet or the stainless steel or the graphite as a cathode and a platinum sheet electrode as an anode, and carrying out the electrodeposition at the temperature of 20 ℃ and the current density of 5-350 mA-cm -2 Under the condition, carrying out electrodeposition for 0.5-4.5 h;
(5) and after the electrodeposition is finished, taking out the sample, washing the sample by using deionized water, performing ultrasonic cleaning, and drying to obtain the Ni-Fe-Cu-Co-W electrocatalyst.
Example 3:
(1) polishing a base material by using 800# to 2000# abrasive paper on a metal iron sheet or stainless steel or graphite with the thickness of 0.08 to 20mm, and activating the polished iron sheet or stainless steel or graphite in 5 to 50 Vol% HCl for 5 to 100 seconds at room temperature; repeatedly washing the activated iron sheet, stainless steel or graphite with deionized water for many times until the pH value is 7 and neutral; carrying out oil removal treatment on iron sheets, stainless steel or graphite by using acetone, cleaning by using deionized water and then drying;
(2) the electrodeposition liquid has a composition of 6 to 75 g.L -1 FeSO 4 ·7H 2 O,110~250g·L -1 Ni 2 SO 4 ·6H 2 O,10~90g·L -1 NiCl 2 ·6H 2 O,15~150g·L -1 CuSO 4 ·5H 2 O,15~150g·L -1 CoSO 4 ·7H 2 O,5~100g·L - 1 Na 2 WO 4 ·2H 2 O,2~50g·L -1 H 3 BO 3 ,5~40g·L -1 Na 3 PO 4 ·12H 2 O,10~300g·L -1 And (3) sodium citrate. Using ammonia water or 2-40 Vol% H 2 SO 4 Adjusting the pH value of the electrodeposition solution to 5-7;
(3) dissolving NiCl 2 ·6H 2 O、Ni 2 SO 4 ·6H 2 Mixing the O solution and the sodium citrate solution, stirring uniformly, and adding H 3 BO 3 Solution and Na 2 WO 4 Adjusting the mixed solutionThe pH value of the solution is 5-7, sodium citrate is added and mixed evenly, and FeSO is added continuously 4 Adjusting the pH value to 5-7, and finally sequentially adding CuSO 4 ·5H 2 O and CoSO 4 ·7H 2 O solution, and adjusting the pH value of the electrodeposition solution to 5-7;
(4) immersing the deoiled iron sheet or stainless steel or graphite into the electrodeposition liquid, taking the iron sheet or the stainless steel or the graphite as a cathode and a platinum sheet electrode as an anode, and carrying out the electrodeposition at the temperature of 30 ℃ and the current density of 5-350 mA-cm -2 Under the condition, carrying out electrodeposition for 0.5-4.5 h;
(5) and after the electrodeposition is finished, taking out the sample, washing the sample by using deionized water, performing ultrasonic cleaning, and drying to obtain the Ni-Fe-Cu-Co-W electrocatalyst.
Example 4:
(1) polishing a base material by using 800# to 2000# abrasive paper on a metal iron sheet or stainless steel or graphite with the thickness of 0.08 to 20mm, and activating the polished iron sheet or stainless steel or graphite in 5 to 50 Vol% HCl for 5 to 100 seconds at room temperature; repeatedly washing the activated iron sheet, stainless steel or graphite with deionized water for many times until the pH value is 7 and neutral; carrying out oil removal treatment on iron sheets, stainless steel or graphite by using acetone, cleaning by using deionized water and then drying;
(2) the electrodeposition liquid has a composition of 6 to 75 g.L -1 FeSO 4 ·7H 2 O,110~250g·L -1 Ni 2 SO 4 ·6H 2 O,10~90g·L -1 NiCl 2 ·6H 2 O,15~150g·L -1 CuSO 4 ·5H 2 O,15~150g·L -1 CoSO 4 ·7H 2 O,5~100g·L - 1 Na 2 WO 4 ·2H 2 O,2~50g·L -1 H 3 BO 3 ,5~40g·L -1 Na 3 PO 4 ·12H 2 O,10~300g·L -1 And (3) sodium citrate. Using ammonia water or 2-40 Vol% H 2 SO 4 Adjusting the pH value of the electrodeposition solution to 5-7;
(3) dissolving NiCl 2 ·6H 2 O、Ni 2 SO 4 ·6H 2 Mixing the O solution and the sodium citrate solution, and uniformly stirringAdding H after mixing 3 BO 3 Solution and Na 2 WO 4 Adjusting the pH value of the mixed solution to 5-7, adding sodium citrate, uniformly mixing, and continuously adding FeSO 4 Adjusting the pH value to 5-7, and finally sequentially adding CuSO 4 ·5H 2 O and CoSO 4 ·7H 2 O solution, and adjusting the pH value of the electrodeposition solution to 5-7;
(4) immersing the deoiled iron sheet or stainless steel or graphite into the electrodeposition liquid, taking the iron sheet or the stainless steel or the graphite as a cathode and a platinum sheet electrode as an anode, and carrying out the electrodeposition at the temperature of 5-35 ℃ and the current density of 50 mA-cm -2 Under the condition, carrying out electrodeposition for 0.5-4.5 h;
(5) and after the electrodeposition is finished, taking out the sample, washing the sample by using deionized water, performing ultrasonic cleaning, and drying to obtain the Ni-Fe-Cu-Co-W electrocatalyst.
Example 5
(1) Polishing a base material by using 800# to 2000# abrasive paper on a metal iron sheet or stainless steel or graphite with the thickness of 0.08 to 20mm, and activating the polished iron sheet or stainless steel or graphite in 5 to 50 Vol% HCl for 5 to 100 seconds at room temperature; repeatedly washing the activated iron sheet, stainless steel or graphite with deionized water for many times until the pH value is 7 and neutral; carrying out oil removal treatment on iron sheets, stainless steel or graphite by using acetone, cleaning by using deionized water and then drying;
(2) the electrodeposition liquid has a composition of 6 to 75 g.L -1 FeSO 4 ·7H 2 O,110~250g·L -1 Ni 2 SO 4 ·6H 2 O,10~90g·L -1 NiCl 2 ·6H 2 O,15~150g·L -1 CuSO 4 ·5H 2 O,15~150g·L -1 CoSO 4 ·7H 2 O,5~100g·L - 1 Na 2 WO 4 ·2H 2 O,2~50g·L -1 H 3 BO 3 ,5~40g·L -1 Na 3 PO 4 ·12H 2 O,10~300g·L -1 And (4) sodium citrate. Using ammonia water or 2-40 Vol% H 2 SO 4 Adjusting the pH value of the electrodeposition solution to 5-7;
(3) dissolving NiCl 2 ·6H 2 O、Ni 2 SO 4 ·6H 2 Mixing the O solution and the sodium citrate solution, stirring uniformly, and adding H 3 BO 3 Solution and Na 2 WO 4 Adjusting the pH value of the mixed solution to 5-7, adding sodium citrate, uniformly mixing, and continuously adding FeSO 4 Adjusting the pH value to 5-7, and finally sequentially adding CuSO 4 ·5H 2 O and CoSO 4 ·7H 2 O solution, and adjusting the pH value of the electrodeposition solution to 5-7;
(4) immersing the deoiled iron sheet or stainless steel or graphite into the electrodeposition liquid, taking the iron sheet or the stainless steel or the graphite as a cathode and a platinum sheet electrode as an anode, and carrying out the electrodeposition at the temperature of 5-35 ℃ and the current density of 100 mA-cm -2 Under the condition, carrying out electrodeposition for 0.5-4.5 h;
(5) and after the electrodeposition is finished, taking out the sample, washing the sample by using deionized water, performing ultrasonic cleaning, and drying to obtain the Ni-Fe-Cu-Co-W electrocatalyst.
Example 6
(1) Polishing a base material by using 800# to 2000# abrasive paper on a metal iron sheet or stainless steel or graphite with the thickness of 0.08 to 20mm, and activating the polished iron sheet or stainless steel or graphite in 5 to 50 Vol% HCl for 5 to 100 seconds at room temperature; repeatedly washing the activated iron sheet, stainless steel or graphite with deionized water for many times until the pH value is 7 and neutral; carrying out oil removal treatment on iron sheets, stainless steel or graphite by using acetone, cleaning by using deionized water and then drying;
(2) the electrodeposition liquid has a composition of 6 to 75 g.L -1 FeSO 4 ·7H 2 O,110~250g·L -1 Ni 2 SO 4 ·6H 2 O,10~90g·L -1 NiCl 2 ·6H 2 O,15~150g·L -1 CuSO 4 ·5H 2 O,15~150g·L -1 CoSO 4 ·7H 2 O,10g·L - 1 Na 2 WO 4 ·2H 2 O,2~50g·L -1 H 3 BO 3 ,5~40g·L -1 Na 3 PO 4 ·12H 2 O,10~300g·L -1 And (3) sodium citrate. Using ammonia water or 2-40 Vol% H 2 SO 4 Adjusting the pH value of the electrodeposition solutionTo 5 to 7;
(3) dissolving NiCl 2 ·6H 2 O、Ni 2 SO 4 ·6H 2 Mixing the O solution and the sodium citrate solution, stirring uniformly, and adding H 3 BO 3 Solution and Na 2 WO 4 Adjusting the pH value of the mixed solution to 5-7, adding sodium citrate, uniformly mixing, and continuously adding FeSO 4 Adjusting the pH value to 5-7, and finally sequentially adding CuSO 4 ·5H 2 O and CoSO 4 ·7H 2 O solution, and adjusting the pH value of the electrodeposition solution to 5-7;
(4) immersing the deoiled iron sheet or stainless steel or graphite into the electrodeposition liquid, taking the iron sheet or stainless steel or graphite as a cathode and a platinum sheet electrode as an anode, and carrying out the electrodeposition at the temperature of 5-35 ℃ and the current density of 5-350 mA-cm -2 Under the condition, carrying out electrodeposition for 0.5-4.5 h;
(5) and after the electrodeposition is finished, taking out the sample, washing the sample by using deionized water, performing ultrasonic cleaning, and drying to obtain the Ni-Fe-Cu-Co-W electrocatalyst.
Example 7
(1) Polishing a base material by using 800# to 2000# abrasive paper on a metal iron sheet or stainless steel or graphite with the thickness of 0.08 to 20mm, and activating the polished iron sheet or stainless steel or graphite in 5 to 50 Vol% HCl for 5 to 100 seconds at room temperature; repeatedly washing the activated iron sheet, stainless steel or graphite with deionized water for many times until the pH value is 7 and neutral; carrying out oil removal treatment on iron sheets, stainless steel or graphite by using acetone, cleaning by using deionized water and then drying;
(2) the electrodeposition liquid has a composition of 6 to 75 g.L -1 FeSO 4 ·7H 2 O,110~250g·L -1 Ni 2 SO 4 ·6H 2 O,10~90g·L -1 NiCl 2 ·6H 2 O,15~150g·L -1 CuSO 4 ·5H 2 O,15~150g·L -1 CoSO 4 ·7H 2 O,15g·L - 1 Na 2 WO 4 ·2H 2 O,2~50g·L -1 H 3 BO 3 ,5~40g·L -1 Na 3 PO 4 ·12H 2 O,10~300g·L -1 And (3) sodium citrate. Using ammonia water or 2-40 Vol% H 2 SO 4 Adjusting the pH value of the electrodeposition solution to 5-7;
(3) dissolving NiCl 2 ·6H 2 O、Ni 2 SO 4 ·6H 2 Mixing the O solution and the sodium citrate solution, stirring uniformly, and adding H 3 BO 3 Solution and Na 2 WO 4 Adjusting the pH value of the mixed solution to 5-7, adding sodium citrate, uniformly mixing, and continuously adding FeSO 4 Adjusting the pH value to 5-7, and finally sequentially adding CuSO 4 ·5H 2 O and CoSO 4 ·7H 2 O solution, and adjusting the pH value of the electrodeposition solution to 5-7;
(4) immersing the deoiled iron sheet or stainless steel or graphite into the electrodeposition liquid, taking the iron sheet or stainless steel or graphite as a cathode and a platinum sheet electrode as an anode, and carrying out the electrodeposition at the temperature of 5-35 ℃ and the current density of 5-350 mA-cm -2 Under the condition, carrying out electrodeposition for 0.5-4.5 h;
(5) and after the electrodeposition is finished, taking out the sample, washing the sample by using deionized water, performing ultrasonic cleaning, and drying to obtain the Ni-Fe-Cu-Co-W electrocatalyst.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the invention and are not to be construed as limiting the invention in any way, and any person skilled in the art may make changes or modifications to the equivalent embodiments using the technical content disclosed above. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (5)
1. A method for preparing a Ni-Fe-Cu-Co-W high-entropy alloy electrocatalyst by an electrodeposition method comprises the following sequential steps:
(1) polishing a base material by using 800# to 2000# abrasive paper on a metal iron sheet or stainless steel or graphite with the thickness of 0.08 to 20mm, and removing macroscopic flaws such as oxide skin, scratches and the like on the surface layer of the base material;
(2) activating the polished iron sheet, stainless steel or graphite in 5-50 Vol% HCl for 5-100 s at room temperature;
(3) repeatedly washing the activated iron sheet, stainless steel or graphite with deionized water for many times until the pH value is 7 and neutral;
(4) carrying out oil removal treatment on iron sheets, stainless steel or graphite by using acetone, cleaning by using deionized water and then drying;
(5) the electrodeposition liquid has a composition of 6 to 75 g.L -1 FeSO 4 ·7H 2 O,110~250g·L -1 Ni 2 SO 4 ·6H 2 O,10~90g·L -1 NiCl 2 ·6H 2 O,15~150g·L -1 CuSO 4 ·5H 2 O,15~150g·L -1 CoSO 4 ·7H 2 O,5~100g·L - 1 Na 2 WO 4 ·2H 2 O,2~50g·L -1 H 3 BO 3 ,5~40g·L -1 Na 3 PO 4 ·12H 2 O,10~300g·L -1 And (3) sodium citrate. Using ammonia water or 2-40 Vol% H 2 SO 4 Adjusting the pH value of the electrodeposition solution to 5-7;
(6) dissolving NiCl 2 ·6H 2 O、Ni 2 SO 4 ·6H 2 Mixing the O solution and the sodium citrate solution, stirring uniformly, and adding H 3 BO 3 Solution and Na 2 WO 4 Adjusting the pH value of the mixed solution to 5-7, adding sodium citrate, uniformly mixing, and continuously adding FeSO 4 Adjusting the pH value to 5-7, and finally sequentially adding CuSO 4 ·5H 2 O and CoSO 4 ·7H 2 O solution, and adjusting the pH value of the electrodeposition solution to 5-7;
(7) immersing the deoiled iron sheet or stainless steel or graphite into the electrodeposition liquid, taking the iron sheet or stainless steel or graphite as a cathode and a platinum sheet electrode as an anode, and carrying out the electrodeposition at a temperature of 5-25 ℃ and a current density of 5-350 mA-cm -2 Under the condition, carrying out electrodeposition for 0.5-4.5 h;
(8) and after the electrodeposition is finished, taking out the sample, washing the sample by using deionized water, performing ultrasonic cleaning, and drying to obtain the Ni-Fe-Cu-Co-W electrocatalyst.
2. The method for preparing the Ni-Fe-Cu-Co-W high-entropy alloy electrocatalyst according to the claim 1, which is characterized in that: polishing metal iron sheets or stainless steel or graphite with the thickness of 0.08-20 mm by using abrasive paper to remove macroscopic flaws, then carrying out activation treatment at room temperature, cleaning the activated iron sheets or stainless steel or graphite by using deionized water, then carrying out oil removal treatment by using acetone, and drying after washing by using deionized water.
3. The method for preparing the Ni-Fe-Cu-Co-W high-entropy alloy electrocatalyst according to the claim 1, which is characterized in that: the electrodeposition liquid has a composition of 6 to 75 g.L -1 FeSO 4 ·7H 2 O,110~250g·L -1 Ni 2 SO 4 ·6H 2 O,10~90g·L -1 NiCl 2 ·6H 2 O,15~150g·L -1 CuSO 4 ·5H 2 O,15~150g·L -1 CoSO 4 ·7H 2 O,5~100g·L - 1 Na 2 WO 4 ·2H 2 O,2~50g·L -1 H 3 BO 3 ,5~40g·L -1 Na 3 PO 4 ·12H 2 O,10~300g·L -1 Sodium citrate with ammonia water or 2-40 Vol% H 2 SO 4 Adjusting the pH value of the electrodeposition solution to 5-7.
4. The method for preparing the Ni-Fe-Cu-Co-W high-entropy alloy electrocatalyst according to the claim 1, which is characterized in that: the adding sequence of each component of the electrodeposition liquid is NiCl 2 ·6H 2 O、Ni 2 SO 4 ·6H 2 O, sodium citrate, H 3 BO 3 、Na 2 WO 4 、FeSO 4 、CuSO 4 ·5H 2 O and CoSO 4 ·7H 2 O solution, ammonia water or 2-40 Vol% H 2 SO 4 Adjusting the pH value of the electrodeposition liquid to be 5-7 all the time.
5. The method for preparing the Ni-Fe-Cu-Co-W high-entropy alloy electrocatalyst by electrodeposition according to claim 1The method is characterized in that: immersing the activated and deoiled iron sheet or stainless steel or graphite into the electrodeposition liquid, taking the iron sheet or stainless steel or graphite as a cathode and a platinum sheet electrode as an anode, and carrying out the treatment at the temperature of 5-25 ℃ and the current density of 5-350 mA-cm -2 Under the condition, carrying out electrodeposition for 0.5-4.5 h, and after the electrodeposition is finished, carrying out ionized water cleaning, ultrasonic cleaning and drying treatment on the sample to prepare the Ni-Fe-Cu-Co-W high-entropy alloy electrocatalyst.
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