CN117721488A - High-entropy alloy catalyst for hydrogen production by alkaline water electrolysis and preparation method thereof - Google Patents
High-entropy alloy catalyst for hydrogen production by alkaline water electrolysis and preparation method thereof Download PDFInfo
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- CN117721488A CN117721488A CN202311738869.1A CN202311738869A CN117721488A CN 117721488 A CN117721488 A CN 117721488A CN 202311738869 A CN202311738869 A CN 202311738869A CN 117721488 A CN117721488 A CN 117721488A
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- 239000000956 alloy Substances 0.000 title claims abstract description 117
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 116
- 239000003054 catalyst Substances 0.000 title claims abstract description 114
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 39
- 239000001257 hydrogen Substances 0.000 title claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims description 156
- 238000004070 electrodeposition Methods 0.000 claims description 101
- 239000000243 solution Substances 0.000 claims description 89
- 239000002184 metal Substances 0.000 claims description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000011734 sodium Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003381 stabilizer Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004327 boric acid Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000001509 sodium citrate Substances 0.000 claims description 9
- 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 description 9
- 241000080590 Niso Species 0.000 claims description 8
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 2
- 239000001508 potassium citrate Substances 0.000 claims description 2
- 229960002635 potassium citrate Drugs 0.000 claims description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 2
- 235000011082 potassium citrates Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 230000008901 benefit Effects 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 description 17
- 238000006460 hydrolysis reaction Methods 0.000 description 17
- 230000008859 change Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000011056 performance test Methods 0.000 description 9
- 238000004502 linear sweep voltammetry Methods 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- -1 salt ions Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention provides a high-entropy alloy catalyst for hydrogen production by alkaline water electrolysis and a preparation method thereof, wherein metal elements in the high-entropy alloy catalyst comprise any five of Fe, ni, co, mn, cu, zn, mg, ti, W or Mo. In the reaction of hydrogen production by alkaline electrolysis of water, the high-entropy alloy catalyst provided by the invention has the advantages that the required electrolysis voltage is lower, the stability is higher, and the catalytic performance of the high-entropy alloy catalyst is not obviously reduced after the high-current density continuous reaction is carried out for 1000 hours; meanwhile, the high-entropy alloy catalyst has the advantages of easily available raw materials and low cost, and therefore, the high-entropy alloy catalyst also has the advantage of low preparation cost.
Description
Technical Field
The invention belongs to the technical field of catalysts, relates to a high-entropy alloy catalyst for hydrogen production by alkaline water electrolysis, and particularly relates to a high-entropy alloy catalyst for hydrogen production by alkaline water electrolysis and a preparation method thereof.
Background
The large-scale use of traditional energy sources has caused the problems of energy crisis, environmental pollution and the like. Hydrogen is taken as an important chemical energy carrier, and is regarded as a clean energy with the most development potential in the 21 st century by virtue of the advantages of high mass energy density (120 MJ/Kg), zero emission, high conversion efficiency and the like. In recent years, various hydrogen production technologies including cracking reforming, biomass cracking, photo/electro-catalytic water cracking, and the like have been widely designed and developed. Among them, electrocatalytic water splitting is a very promising approach. The electrocatalytic water decomposition consists of a cathodic hydrogen evolution reaction (Hydrogen Evolution Reaction, HER) and an anodic oxygen evolution reaction (Oxygen Evolution Reaction, OER). Currently, platinum carbon (Pt/C) is considered the best performing HER catalyst. Iridium oxide (IrO) 2 ) And ruthenium oxide (RuO) 2 ) By virtue of its unique electronic structure, it is considered to be the best performing OER catalyst. However, these catalysts have the disadvantages of high cost, easy corrosion, etc., and limit the practical application thereof.
CN117070782a discloses a low-Pt high-entropy alloy water electrolysis catalyst, a preparation method and application thereof, 5 metal elements of any one of Mn, ni, cu, pt and La, mo, co, V, ti are selected for combination preparation, the process does not need to adjust the pH, the process is simple, the operation is simple and convenient, the preparation cost is low, industrial production can be realized, and the prepared mnnicurt (La, mo, co, V, ti) high-entropy alloy catalyst has excellent water electrolysis performance, not only reduces the catalyst cost, but also improves the catalytic performance. However, the Pt high-entropy alloy electrolyzed water catalyst still contains Pt element, which has a problem of high cost.
CN116219480a discloses a high-entropy alloy electrolytic water catalyst and a preparation method thereof, the preparation method comprises: mixing, drying and thermally shocking the metal salt solution, the nitrogen source and the carbon material to obtain the high-entropy alloy electrolyzed water catalyst; the mass ratio of nitrogen element to carbon material in the nitrogen source is (1-5) 20; the high-entropy alloy electrolyzed water catalyst comprises at least 5 metal elements. The metal salt of the metal salt solution is reduced into simple substances under the action of the carbon material, and then the simple substances are combined together to form an alloy by utilizing a thermal shock method, so that the agglomeration of alloy particles can be prevented, the structural uniformity of the alloy particles is maintained, and the occurrence of phase segregation is avoided; the carbon material is also used as a carrier to improve the conductivity of the high-entropy alloy electrolyzed water catalyst, and nitrogen element doping modification is carried out on the carbon material by adding a nitrogen source, so that the interaction between metal and the carrier is enhanced, and the catalytic activity and stability are further improved; the preparation method has simple process and short time, and is beneficial to realizing large-scale production. However, the high-entropy alloy electrolytic water catalyst has poor corrosion resistance and short service life.
The high-entropy alloy catalyst disclosed at present has certain defects, and has the problems of higher preparation cost and poorer corrosion resistance. Therefore, the development and design of a novel high-entropy alloy catalyst for hydrogen production by alkaline water electrolysis are important.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a high-entropy alloy catalyst for hydrogen production by alkaline water electrolysis and a preparation method thereof, and the high-entropy alloy catalyst provided by the invention has lower required electrolysis voltage, higher stability and high current density (500-1000 mA/cm 2 ) After the reaction is continued for 1000 hours, the catalytic performance of the high-entropy alloy catalyst is not obviously reduced; meanwhile, the high-entropy alloy catalyst has the advantages of easily available raw materials and low cost, and therefore, the high-entropy alloy catalyst also has the advantage of low preparation cost.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a high-entropy alloy catalyst for hydrogen production by alkaline electrolysis of water, wherein the metal elements in the high-entropy alloy catalyst comprise any five of Fe, ni, co, mn, cu, zn, mg, ti, W or Mo.
The metal elements in the high-entropy alloy catalyst in the invention comprise any five of Fe, ni, co, mn, cu, zn, mg, ti, W and Mo, for example, fe, ni, co, mn and Cu, co, mn, cu, zn and Mg, zn, mg, ti, W and Mo, ni, co, mn, cu and Zn, or Mn, cu, zn, mg and Ti.
The high-entropy alloy is used as a novel alloy material and is a material composed of at least five metal elements with the same or similar molar ratio. Compared with the traditional alloy, the high-entropy alloy has the characteristics of high disorder structure, high stability, adjustable components and electronic structure and the like. These characteristics make the high-entropy alloy have great potential for application in the electrochemical catalysis field; in addition, the non-noble metal high-entropy alloy has the advantages of low price, high activity and the like, and various metal elements interact with each other, so that the non-noble metal high-entropy alloy has high activity and controllability; therefore, the high-entropy alloy is used as a catalyst for hydrogen production by alkaline water electrolysis.
The high-entropy alloy catalyst provided by the invention has the advantages of lower required electrolysis voltage, higher stability and high current density (500-1000 mA/cm) in the reaction of hydrogen production by alkaline electrolysis of water 2 ) After the reaction is continued for 1000 hours, the catalytic performance of the high-entropy alloy catalyst is not obviously reduced; meanwhile, the high-entropy alloy catalyst has the advantages of easily available raw materials and low cost, and therefore, the high-entropy alloy catalyst also has the advantage of low preparation cost.
In a second aspect, the present invention provides a method for preparing the high-entropy alloy catalyst according to the first aspect, the method comprising:
placing a carrier in an electrodeposition solution, and obtaining the high-entropy alloy catalyst through electrodeposition;
the electrodeposition solution includes a metal salt including any five of a Fe salt, a Ni salt, a Co salt, a Mn salt, a Cu salt, a Zn salt, a Mg salt, a Ti salt, a W salt, or a Mo salt.
The metal salt in the present invention includes any five of Fe salt, ni salt, co salt, mn salt, cu salt, zn salt, mg salt, ti salt, W salt, or Mo salt, and may be, for example, a combination of Fe salt, ni salt, co salt, mn salt, and Cu salt, a combination of Ni salt, co salt, mn salt, cu salt, and Zn salt, a combination of Mn salt, cu salt, zn salt, mg salt, and Ti salt, a combination of Zn salt, mg salt, ti salt, W salt, and Mo salt, or a combination of Cu salt, zn salt, mg salt, ti salt, and W salt.
The preparation method of the high-entropy alloy catalyst provided by the invention has the advantages of simple process, low operation difficulty, low requirements on production equipment and easiness in large-scale popularization and use.
Preferably, the difference between the highest and lowest values of the concentrations of the five salts included in the electrodeposition solution is not higher than 0.3mol/L, and may be, for example, 0.3mol/L, 0.28mol/L, 0.26mol/L, 0.24mol/L, 0.22mol/L, 0.2mol/L, 0.18mol/L, 0.16mol/L, 0.14mol/L, 0.12mol/L, 0.1mol/L, 0.08mol/L, 0.06mol/L, 0.04mol/L, 0.02mol/L or 0.01mol/L, but not limited to the recited values, and other non-recited values within this range of values are equally applicable.
The concentration of Fe salt in the electrodeposition solution is preferably 0.01 to 0.5mol/L, and may be, for example, 0.01mol/L, 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, or 0.5mol/L, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The concentration of Ni salt in the electrodeposition solution is preferably 0.01 to 0.5mol/L, and may be, for example, 0.01mol/L, 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, or 0.5mol/L, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The concentration of Co salt in the electrodeposition solution is preferably 0.01 to 0.5mol/L, and may be, for example, 0.01mol/L, 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, or 0.5mol/L, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The concentration of Mn salt in the electrodeposition solution is preferably 0.01 to 0.5mol/L, and may be, for example, 0.01mol/L, 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, or 0.5mol/L, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The concentration of the Cu salt in the electrodeposition solution is preferably 0.01 to 0.5mol/L, and may be, for example, 0.01mol/L, 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, or 0.5mol/L, but is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
The concentration of Zn salt in the electrodeposition solution is preferably 0.01 to 0.5mol/L, and may be, for example, 0.01mol/L, 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L or 0.5mol/L, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The concentration of Mg salt in the electrodeposition solution is preferably 0.01 to 0.5mol/L, and may be, for example, 0.01mol/L, 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, or 0.5mol/L, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The concentration of Ti salt in the electrodeposition solution is preferably 0.01 to 0.5mol/L, and may be, for example, 0.01mol/L, 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, or 0.5mol/L, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
The concentration of the W salt in the electrodeposition solution is preferably 0.01 to 0.5mol/L, and may be, for example, 0.01mol/L, 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, or 0.5mol/L, but is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
The concentration of the Mo salt in the electrodeposition solution is preferably 0.01 to 0.5mol/L, and may be, for example, 0.01mol/L, 0.02mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L or 0.5mol/L, but is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
Preferably, the Fe salt comprises FeSO 4 、FeCl 2 Or Fe (NO) 3 ) 2 Any one or more ofCombinations of at least two, typically but not limited to FeSO 4 With FeCl 2 FeCl 2 With Fe (NO) 3 ) 2 FeSO, combinations of (C) and (B) 4 With Fe (NO) 3 ) 2 Or FeSO 4 、FeCl 2 With Fe (NO) 3 ) 2 Is a combination of (a) and (b).
Preferably, the Ni salt comprises NiSO 4 、NiCl 2 Or Ni (NO) 3 ) 2 Any one or a combination of at least two, typically but not limited to NiSO 4 With NiCl 2 NiCl 2 With Ni (NO) 3 ) 2 Or NiSO 4 、NiCl 2 With Ni (NO) 3 ) 2 Is a combination of (a) and (b).
Preferably, the Co salt comprises CoSO 4 、CoCl 2 Or Co (NO) 3 ) 2 Any one or a combination of at least two, typically but not limited to a combination including CoSO 4 With CoCl 2 Is a combination of (C) and (C) CoCl 2 With Co (NO) 3 ) 2 Or CoSO 4 、CoCl 2 With Co (NO) 3 ) 2 Is a combination of (a) and (b).
Preferably, the Mn salt comprises MnSO 4 、MnCl 2 Or Mn (NO) 3 ) 2 Any one or a combination of at least two, typically but not limited to MnSO 4 With MnCl 2 Is a combination of MnCl 2 With Mn (NO) 3 ) 2 Or MnSO 4 、MnCl 2 With Mn (NO) 3 ) 2 Is a combination of (a) and (b).
Preferably, the Cu salt comprises CuSO 4 、CuCl 2 Or Cu (NO) 3 ) 2 Any one or a combination of at least two, typically but not limited to CuSO 4 With CuCl 2 CuCl 2 With Cu (NO) 3 ) 2 Or CuSO 4 、CuCl 2 With Cu (NO) 3 ) 2 Is a combination of (a) and (b).
Preferably, the Zn salt comprises ZnSO 4 、ZnCl 2 Or Zn (NO) 3 ) 2 Any one or a combination of at least two, typically but not limited to a combination comprising ZnSO 4 With ZnCl 2 ZnCl combination 2 With Zn (NO) 3 ) 2 Or ZnSO 4 、ZnCl 2 With Zn (NO) 3 ) 2 Is a combination of (a) and (b).
Preferably, the Mg salt comprises MgSO 4 、MgCl 2 Or Mg (NO) 3 ) 2 Any one or a combination of at least two, typically but not limited to, mgSO 4 With MgCl 2 Is MgCl 2 With Mg (NO) 3 ) 2 Or MgSO 4 、MgCl 2 With Mg (NO) 3 ) 2 Is a combination of (a) and (b).
Preferably, the Ti salt comprises Ti (SO 4 ) 2 、TiCl 4 Or TiO (acac) 2 Any one or a combination of at least two, typically but not limited to, a combination comprising Ti (SO 4 ) 2 With TiCl 4 TiCl, combinations of (a) and (b) 4 And TiO (acac) 2 Is a combination of Ti (SO) 4 ) 2 、TiCl 4 And TiO (acac) 2 Is a combination of (a) and (b).
Preferably, the W salt comprises Na 2 WO 4 、(NH 4 ) 2 WO 2 Cl 4 、Na 2 WO 2 Cl 4 Any one or a combination of at least two, typically but not limited to, na 2 WO 4 And (NH) 4 ) 2 WO 2 Cl 4 Combinations of (NH) 4 ) 2 WO 2 Cl 4 With Na and Na 2 WO 2 Cl 4 Or Na of (C) 2 WO 4 、(NH 4 ) 2 WO 2 Cl 4 With Na and Na 2 WO 2 Cl 4 Is a combination of (a) and (b).
Preferably, the Mo salt comprises Na 2 MoO 4 、(NH 4 ) 6 Mo 7 O 24 Or (NH) 4 ) 2 MoOCl 5 Any one or a combination of at least two, typically but not limited to, na 2 MoO 4 And (NH) 4 ) 6 Mo 7 O 24 Combinations of (NH) 4 ) 6 Mo 7 O 24 And (NH) 4 ) 2 MoOCl 5 Or Na of (C) 2 MoO 4 、(NH 4 ) 6 Mo 7 O 24 And (NH) 4 ) 2 MoOCl 5 Is a combination of (a) and (b).
Preferably, the carrier comprises any one of conductive glass, foam nickel, carbon paper, carbon cloth or woven nickel mesh.
Preferably, the method of preparing the electrodeposition solution comprises:
mixing the metal salt with a solvent to obtain a primary mixed solution, mixing the primary mixed solution with a regulator and a stabilizer to obtain a remixed solution, and regulating the remixed solution to a set pH value by using acid and/or alkali to obtain the electrodeposition solution.
Preferably, the solvent comprises water.
Preferably, the modifier comprises any one or a combination of at least two of boric acid, silicic acid or acetic acid, typically but not limited to a combination of boric acid and silicic acid, a combination of silicic acid and acetic acid, a combination of boric acid and acetic acid, or a combination of boric acid, silicic acid and acetic acid.
The concentration of the regulator in the electrodeposition solution is preferably 0.5 to 2mol/L, and may be, for example, 0.5mol/L, 0.7mol/L, 0.9mol/L, 1mol/L, 1.2mol/L, 1.4mol/L, 1.6mol/L, 1.8mol/L, or 2mol/L, but is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
Preferably, the stabilizer comprises sodium citrate and/or potassium citrate.
The concentration of the stabilizer in the electrodeposition solution is preferably 0.1 to 0.5mol/L, and may be, for example, 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.35mol/L, 0.4mol/L, 0.45mol/L, or 0.5mol/L, but is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
Preferably, the acid comprises any one or a combination of at least two of sulfuric acid, hydrochloric acid or nitric acid, typically but not limited to a combination of sulfuric acid and hydrochloric acid, a combination of hydrochloric acid and nitric acid, a combination of sulfuric acid, hydrochloric acid and nitric acid.
Preferably, the base comprises sodium hydroxide and/or potassium hydroxide.
Preferably, the set pH is 2 to 10, and may be, for example, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5 or 10, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the electrodeposition includes constant current electrodeposition, constant voltage electrodeposition or pulsed voltage electrodeposition.
Preferably, the electric potential of the electrodeposition is-0.6 to-2V for 100 to 7200s.
The potential of the electrodeposition according to the present invention is-0.6 to-2V, and may be, for example, -0.6V, -0.7V, -0.8V, -0.9V, -1V, -1.1V, -1.2V, -1.3V, -1.4V, -1.5V, -1.6V, -1.7V, -1.8V, -1.9V or-2V, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the pulse voltage electrodeposition interval is 1 to 10s, for example, 1s, 1.5s, 2s, 2.5s, 3s, 3.5s, 4s, 4.5s, 5s, 5.5s, 6s, 6.5s, 7s, 7.5s, 8s, 8.5s, 9s, 9.5s or 10s, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the preparation method further comprises washing and drying sequentially performed after the electrodeposition.
Preferably, the solution used for the washing comprises water and/or ethanol.
Preferably, the drying method comprises infrared lamp irradiation or vacuum drying.
As a preferable technical scheme of the preparation method, the preparation method comprises the following steps:
mixing the metal salt with water to obtain a primary mixed solution, mixing the primary mixed solution with a regulator with the concentration of 0.5-2 mol/L and a stabilizer with the concentration of 0.1-0.5 mol/L to obtain a remixed solution, and regulating the remixed solution to pH value of 2-10 by using acid and/or alkali to obtain the electrodeposition solution; placing any one of conductive glass, foam nickel, carbon paper, carbon cloth or woven nickel screen into an electrodeposition solution, performing electrodeposition for 100-7200 s at a potential of-0.6V to-2V, washing with water and/or ethanol, and drying by irradiation of an infrared lamp or vacuum drying to obtain the high-entropy alloy catalyst;
the electrodeposition solution includes a metal salt including any five of an Fe salt having a concentration of 0.01 to 0.5mol/L, a Ni salt having a concentration of 0.01 to 0.5mol/L, a Co salt having a concentration of 0.01 to 0.5mol/L, an Mn salt having a concentration of 0.01 to 0.5mol/L, a Cu salt having a concentration of 0.01 to 0.5mol/L, a Zn salt having a concentration of 0.01 to 0.5mol/L, a Mg salt having a concentration of 0.01 to 0.5mol/L, a Ti salt having a concentration of 0.01 to 0.5mol/L, a W salt having a concentration of 0.01 to 0.5mol/L, or a Mo salt having a concentration of 0.01 to 0.5mol/L, and a difference between the highest concentration and the lowest concentration of the five salts included in the electrodeposition solution is not higher than 0.3mol/L.
Compared with the prior art, the invention has the following beneficial effects:
the high-entropy alloy catalyst provided by the invention has the advantages of lower required electrolysis voltage, higher stability and high current density (500-1000 mA/cm) in the reaction of hydrogen production by alkaline electrolysis of water 2 ) After the reaction is continued for 1000 hours, the catalytic performance of the high-entropy alloy catalyst is not obviously reduced; meanwhile, the high-entropy alloy catalyst has the advantages of easily available raw materials and low cost, and therefore, the high-entropy alloy catalyst also has the advantage of low preparation cost.
Drawings
Fig. 1 is a TEM image of the high entropy alloy catalyst in example 1.
Fig. 2 is an LSV curve of OER for the high entropy alloy catalyst of example 1.
Fig. 3 is a LSV curve of HER for the high entropy alloy catalyst of example 1.
FIG. 4 is a LSV plot of the perhydrolysis performance of the high-entropy alloy catalyst of example 1.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a high-entropy alloy catalyst for hydrogen production by alkaline water electrolysis, wherein metal elements in the high-entropy alloy catalyst comprise Fe, ni, co, mn and Cu;
the preparation method of the high-entropy alloy catalyst comprises the following steps:
mixing the metal salt with water to obtain a primary mixed solution, mixing the primary mixed solution with boric acid with the concentration of 1.2mol/L and sodium citrate with the concentration of 0.3mol/L to obtain a remixed solution, and regulating the remixed solution to pH 3 by using sulfuric acid to obtain the electrodeposition solution; placing foam nickel into an electrodeposition solution, performing electrodeposition for 3600s at a potential of-1.3V, washing with ethanol, and drying by irradiation of an infrared lamp to obtain the high-entropy alloy catalyst;
the electrodeposition solution comprises a metal salt comprising FeSO at a concentration of 0.1mol/L 4 NiSO with concentration of 0.1mol/L 4 CoSO with concentration of 0.1mol/L 4 MnSO with concentration of 0.1mol/L 4 And CuSO with concentration of 0.1mol/L 4 。
Example 2
The embodiment provides a high-entropy alloy catalyst for hydrogen production by alkaline water electrolysis, wherein metal elements in the high-entropy alloy catalyst comprise Co, mn, cu, zn and Mg;
the preparation method of the high-entropy alloy catalyst comprises the following steps:
mixing the metal salt with water to obtain a primary mixed solution, mixing the primary mixed solution with boric acid with the concentration of 0.8mol/L and sodium citrate with the concentration of 0.4mol/L to obtain a remixed solution, and adjusting the remixed solution to pH value of 2 by using hydrochloric acid to obtain the electrodeposition solution; placing conductive glass in an electrodeposition solution, performing electrodeposition for 5200s at a potential of-1V, washing with water, and drying by vacuum drying to obtain the high-entropy alloy catalyst;
the electrodeposition solution comprises a metal salt comprising CoCl at a concentration of 0.05mol/L 2 MnCl with concentration of 0.05mol/L 2 CuCl with concentration of 0.05mol/L 2 ZnCl with concentration of 0.05mol/L 2 And MgCl with concentration of 0.05mol/L 2 。
Example 3
The embodiment provides a high-entropy alloy catalyst for hydrogen production by alkaline water electrolysis, wherein metal elements in the high-entropy alloy catalyst comprise Cu, zn, mg, ti and W;
the preparation method of the high-entropy alloy catalyst comprises the following steps:
mixing the metal salt with water to obtain a primary mixed solution, mixing the primary mixed solution with boric acid with the concentration of 1.6mol/L and sodium citrate with the concentration of 0.2mol/L to obtain a remixed solution, and adjusting the remixed solution to pH 9 by using sodium hydroxide to obtain the electrodeposition solution; placing carbon paper in an electrodeposition solution, performing electrodeposition for 1500 seconds at a potential of-1.6V, washing with ethanol, and drying by irradiation of an infrared lamp to obtain the high-entropy alloy catalyst;
the electrodeposition solution comprises a metal salt comprising CuSO at a concentration of 0.3mol/L 4 ZnSO with concentration of 0.3mol/L 4 MgSO with concentration of 0.1mol/L 4 Ti (SO) at a concentration of 0.3mol/L 4 ) 2 And Na at a concentration of 0.3mol/L 2 WO 4 。
Example 4
The embodiment provides a high-entropy alloy catalyst for hydrogen production by alkaline water electrolysis, wherein metal elements in the high-entropy alloy catalyst comprise any five of Zn, mg, ti, W and Mo;
the preparation method of the high-entropy alloy catalyst comprises the following steps:
mixing the metal salt with water to obtain a primary mixed solution, mixing the primary mixed solution with boric acid with the concentration of 0.5mol/L and sodium citrate with the concentration of 0.5mol/L to obtain a remixed solution, and adjusting the remixed solution to pH value of 10 by using sodium hydroxide to obtain the electrodeposition solution; placing a woven nickel screen into an electrodeposition solution, performing electrodeposition for 7200s at a potential of-0.6V, washing with water, and drying by vacuum drying to obtain the high-entropy alloy catalyst;
the electrodeposition solution comprises a metal salt comprising Zn (NO) at a concentration of 0.01mol/L 3 ) 2 Mg (NO) at a concentration of 0.01mol/L 3 ) 2 TiCl with concentration of 0.01mol/L 4 Na at a concentration of 0.01mol/L 2 WO 2 Cl 4 Na with concentration of 0.01mol/L 2 MoO 4 。
Example 5
The embodiment provides a high-entropy alloy catalyst for hydrogen production by alkaline water electrolysis, wherein metal elements in the high-entropy alloy catalyst comprise Fe, ni, zn, mg and Ti;
the preparation method of the high-entropy alloy catalyst comprises the following steps:
mixing the metal salt with water to obtain a primary mixed solution, mixing the primary mixed solution with boric acid with the concentration of 2mol/L and sodium citrate with the concentration of 0.1mol/L to obtain a remixed solution, and adjusting the remixed solution to pH value of 5 by using nitric acid to obtain the electrodeposition solution; placing carbon paper in an electrodeposition solution, performing electrodeposition for 100s at a potential of-2V, washing with ethanol, and drying by irradiation of an infrared lamp to obtain the high-entropy alloy catalyst;
the electrodeposition solution comprises a metal salt comprising FeSO at a concentration of 0.5mol/L 4 Ni (NO) at a concentration of 0.5mol/L 3 ) 2 ZnSO with concentration of 0.5mol/L 4 Mg (NO) at a concentration of 0.5mol/L 3 ) 2 And Ti (SO) at a concentration of 0.5mol/L 4 ) 2 。
Example 6
This example provides a high entropy alloy catalyst for hydrogen production by alkaline electrolysis of water, except that the metal salt comprises FeSO at a concentration of 0.45mol/L 4 FeSO comprised by the metal salt in the electrodeposition solution 4 The procedure of example 1 was repeated except that the concentration difference with other salts was higher than 0.3mol/L.
Example 7
The present embodiment provides aHigh entropy alloy catalyst for alkaline water electrolysis hydrogen production, except that the metal salt comprises FeSO with concentration of 0.005mol/L 4 NiSO with concentration of 0.005mol/L 4 CoSO with concentration of 0.005mol/L 4 MnSO with concentration of 0.005mol/L 4 CuSO with concentration of 0.005mol/L 4 Except for this, the procedure was the same as in example 1.
Example 8
This example provides a high entropy alloy catalyst for hydrogen production by alkaline electrolysis of water, except that the metal salt comprises FeSO at a concentration of 0.6mol/L 4 NiSO with concentration of 0.6mol/L 4 CoSO with concentration of 0.6mol/L 4 MnSO with concentration of 0.6mol/L 4 CuSO with concentration of 0.6mol/L 4 Except for this, the procedure was the same as in example 1.
Example 9
This example provides a high entropy alloy catalyst for hydrogen production by alkaline electrolysis of water, which is the same as example 1 except that the concentration of boric acid is 0.3mol/L.
Example 10
This example provides a high entropy alloy catalyst for hydrogen production by alkaline electrolysis of water, which is the same as example 1 except that the concentration of boric acid is 2.5 mol/L.
Example 11
This example provides a high entropy alloy catalyst for hydrogen production by alkaline electrolysis of water, which is the same as example 1 except that the concentration of sodium citrate is 0.05 mol/L.
Example 12
This example provides a high entropy alloy catalyst for hydrogen production by alkaline electrolysis of water, which is the same as example 1 except that the concentration of sodium citrate is 0.8 mol/L.
Example 13
This example provides a high entropy alloy catalyst for hydrogen production by alkaline electrolysis of water, the remainder being the same as example 1, except that electrodeposition is carried out at a potential of-2.4V.
Example 14
This example provides a high entropy alloy catalyst for hydrogen production by alkaline electrolysis of water, the remainder being the same as example 1, except that electrodeposition is carried out at a potential of-0.2V.
Comparative example 1
This comparative example provides an alloy catalyst for alkaline water electrolysis to produce hydrogen, except for omitting FeSO comprised of metal salts in the electrodeposition solution 4 That is, the high-entropy alloy catalyst was the same as in example 1 except that only four metal elements of Ni, co, mn and Cu were included.
Comparative example 2
This comparative example provides an alloy catalyst for alkaline water electrolysis to produce hydrogen, except for omitting NiSO included in the metal salt in the electrodeposition solution 4 The procedure of example 1 was repeated except that the high-entropy alloy catalyst contained only four metal elements of Fe, co, mn and Cu.
Transmission electron microscopy was performed on the high-entropy alloy catalyst of example 1, and a TEM image of the high-entropy alloy catalyst of example 1 is shown in fig. 1.
HER performance test, OER performance test, full hydrolysis performance test and stability test were performed on the high entropy alloy catalysts of examples 1 to 14 and comparative examples 1 and 2;
the test method for the HER performance test and the OER performance test comprises the following steps: pouring 1mol/L KOH solution as electrolyte into a single-chamber electrolytic cell, performing performance test by adopting a three-electrode system, wherein the working electrode is the high-entropy alloy catalyst in examples 1-14 and comparative examples 1 and 2, the reference electrode is Hg/HgO, the counter electrode is a carbon rod, testing the HER and OER performances of the catalyst by a linear sweep voltammetry, and testing to obtain the current density of 100mA/cm 2 When the HER overpotential and OER overpotential of the high-entropy alloy catalysts of examples 1 to 14 and comparative examples 1 and 2 are shown in Table 1; the LSV curve of OER tested for the high-entropy alloy catalyst of example 1 is shown in FIG. 2 and the LSV curve of HER is shown in FIG. 3
The method for testing the full hydrolysis performance comprises the following steps: 1mol/L KOH solution was poured as an electrolyte into an H-type electrolytic cell, and the anode and the cathode were both high-entropy alloy catalysts in examples 1 to 14 and comparative examples 1 and 2, and were evaluated by linear sweep voltammetryThe total hydrolysis performance of the catalyst is tested to obtain the current density of 100mA/cm 2 The required voltages are shown in table 1; the LSV curve tested to give the full hydrolysis performance of the high entropy alloy catalyst of example 1 is shown in fig. 4;
the method for testing the stability comprises the following steps: at a high current density of 500mA/cm 2 After the reaction is continued for 1000 hours, carrying out HER performance test, OER performance test and full hydrolysis performance test again, wherein the HER overpotential, OER overpotential and current density obtained by the test are 100mA/cm 2 After the required voltage, calculating to obtain the HER change rate, OER change rate and voltage change rate as shown in table 2, wherein the change rate of the HER overpotential is shown by = |after-before-reaction HER overpotential/before-reaction HER overpotential; OER overpotential change rate= | OER overpotential after reaction-OER overpotential before reaction/OER overpotential before reaction; voltage change rate= |post-reaction voltage-pre-reaction voltage|/pre-reaction voltage;
TABLE 1
| HER overpotential (mV) | OER overpotential (mV) | Voltage (V) | |
| Example 1 | 173 | 290 | 1.7 |
| Example 2 | 183 | 292 | 1.72 |
| Example 3 | 192 | 293 | 1.73 |
| Example 4 | 187 | 293 | 1.75 |
| Example 5 | 180 | 290 | 1.73 |
| Example 6 | 199 | 310 | 1.79 |
| Example 7 | 195 | 307 | 1.80 |
| Example 8 | 193 | 293 | 1.75 |
| Example 9 | 194 | 294 | 1.76 |
| Implementation of the embodimentsExample 10 | 191 | 293 | 1.74 |
| Example 11 | 190 | 295 | 1.77 |
| Example 12 | 196 | 300 | 1.75 |
| Example 13 | 192 | 302 | 1.79 |
| Example 14 | 198 | 301 | 1.82 |
| Comparative example 1 | 220 | 325 | 1.9 |
| Comparative example 2 | 215 | 330 | 1.88 |
TABLE 2
From tables 1 and 2, it is possible to:
(1) The high-entropy alloy catalyst for alkaline water electrolysis hydrogen production provided by the application shows smaller HER overpotential and smaller OER overpotential in alkaline water electrolysis hydrogen production, and has a current density of 100mA/cm 2 The required full hydrolysis voltage is smaller, and the HER change rate, OER change rate and full hydrolysis voltage change rate after continuous reaction of high current density are smaller;
(2) As is clear from a comparison of example 1 and example 6, the difference in concentration between the highest concentration of the metal salt and the lowest concentration of the salt in the electrodeposition solution in the present invention affects the performance of the high-entropy alloy catalyst; when the concentration difference is larger, the HER overpotential is larger, the OER overpotential is larger, the full hydrolysis voltage is larger, and the HER change rate, the OER change rate and the full hydrolysis voltage change rate after continuous reaction of high current density are larger, because the reduction amount of metal ions of the salt with the lowest concentration is smaller and the ratio of the metal ions in the alloy is lower under the same electrodeposition time when the concentration difference is larger, thereby influencing the performance of the catalyst;
(3) From a comparison of example 1 with examples 7 and 8, it is understood that the concentration of the salt in the metal salt in the electrodeposition solution of the present invention affects the performance of the high entropy alloy catalyst; when the concentration of all the metal salts in the electrodeposition solution is lower, HER overpotential becomes larger and OER overpotential becomes larger, because the reduced alloy amount on the carrier is less under the same electrodeposition time when the concentration of all the metal salts is lower, and the catalytic performance is affected; when the concentration of all the metal salts in the electrodeposition solution is higher, HER overpotential becomes larger, OER overpotential is not changed much and full hydrolysis voltage becomes larger, because the concentration of all the metal salts is higher, and alloy reduced on the carrier is too much under the same electrodeposition time, thus preventing the performance of the catalyst;
(4) From a comparison of example 1 with examples 9 and 10, it is clear that the concentration of the modifier in the present invention affects the performance of the high entropy alloy catalyst; when the concentration of the regulator in the electrodeposition solution is low, HER overpotential is increased, OER overpotential is not changed greatly, and full hydrolysis voltage is increased, because the PH of the electrolyte is changed in the electrodeposition process when the concentration of the regulator is low, which is not beneficial to the synthesis of the catalyst; when the concentration of the regulator in the electrodeposition solution is higher, HER overpotential becomes larger, OER overpotential is not changed much, and full hydrolysis voltage becomes larger, because crystals are easy to be separated out when the concentration of the regulator is higher, which is not beneficial to the synthesis of the catalyst;
(5) From a comparison of example 1 with examples 11 and 12, it is clear that the concentration of the stabilizer in the present invention affects the performance of the high entropy alloy catalyst; when the concentration of the stabilizer is low, HER overpotential is increased, OER overpotential is increased, and full hydrolysis voltage is increased, because the concentration of the stabilizer is low, the PH of the solution is changed in the reduction process, and the catalyst synthesis is not facilitated; when the concentration of the stabilizer is higher, HER overpotential, OER overpotential and full hydrolysis voltage become larger, because the reduction of metal ions is hindered when the concentration of the stabilizer is higher;
(6) As can be seen from a comparison of example 1 with examples 13 and 14, the voltage in electrodeposition in the present invention affects the performance of the high entropy alloy catalyst; when the voltage in the electrodeposition is lower, the HER overpotential is increased, the OER overpotential is increased, the full hydrolysis voltage is increased, and the HER change rate, the OER change rate and the full hydrolysis voltage change rate after continuous reaction of high current density are increased, because when the electrodeposition voltage is lower, certain metal salt ions cannot be reduced, the obtained alloy is not a high-entropy alloy, and the catalytic performance is unstable; when the voltage in the electrodeposition is higher, HER overpotential is increased, OER overpotential is not changed greatly, and full hydrolysis voltage is increased, because a large amount of alloy is reduced on the carrier under the same deposition time when the electrodeposition voltage is higher, so that the overall performance of the catalyst is inhibited;
(7) As is clear from the comparison of example 1 and comparative examples 1 and 2, the high-entropy alloy catalyst provided in the present invention requires lower electrolysis voltage and higher stability in the reaction of hydrogen production by alkaline electrolysis of water, and has high current density (500-1000 mA/cm 2 ) After the reaction is continued for 1000 hours, the catalytic performance of the high-entropy alloy catalyst is not obviously reduced; meanwhile, the high-entropy alloy catalyst has the advantages of easily available raw materials and low cost, and therefore, the high-entropy alloy catalyst also has the advantage of low preparation cost.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.
Claims (10)
1. A high-entropy alloy catalyst for hydrogen production by alkaline water electrolysis, which is characterized in that metal elements in the high-entropy alloy catalyst comprise any five of Fe, ni, co, mn, cu, zn, mg, ti, W or Mo.
2. A method of preparing the high entropy alloy catalyst of claim 1, comprising:
placing a carrier in an electrodeposition solution, and obtaining the high-entropy alloy catalyst through electrodeposition;
the electrodeposition solution includes a metal salt including any five of a Fe salt, a Ni salt, a Co salt, a Mn salt, a Cu salt, a Zn salt, a Mg salt, a Ti salt, a W salt, or a Mo salt.
3. The method according to claim 2, wherein the difference between the highest and lowest values of the concentrations of the five salts included in the metal salt in the electrodeposition solution is not more than 0.3mol/L;
the concentration of Fe salt in the electrodeposition solution is 0.01-0.5 mol/L;
preferably, the concentration of Ni salt in the electrodeposition solution is 0.01-0.5 mol/L;
preferably, the concentration of Co salt in the electrodeposition solution is 0.01-0.5 mol/L;
preferably, the concentration of Mn salt in the electrodeposition solution is 0.01 to 0.5mol/L;
preferably, the concentration of Cu salt in the electrodeposition solution is 0.01-0.5 mol/L;
preferably, the concentration of Zn salt in the electrodeposition solution is 0.01-0.5 mol/L;
preferably, the concentration of Mg salt in the electrodeposition solution is 0.01-0.5 mol/L;
preferably, the concentration of Ti salt in the electrodeposition solution is 0.01-0.5 mol/L;
preferably, the concentration of W salt in the electrodeposition solution is 0.01-0.5 mol/L;
preferably, the concentration of Mo salt in the electrodeposition solution is 0.01 to 0.5mol/L.
4. A method according to claim 2 or 3, wherein the Fe salt comprises FeSO 4 、FeCl 2 Or Fe (NO) 3 ) 2 Any one or a combination of at least two of the following;
preferably, the Ni salt comprises NiSO 4 、NiCl 2 Or Ni (NO) 3 ) 2 Any one or a combination of at least two of the following;
preferably, the Co salt comprises CoSO 4 、CoCl 2 Or Co (NO) 3 ) 2 Any one or a combination of at least two of the following;
preferably, the Mn salt comprises MnSO 4 、MnCl 2 Or Mn (NO) 3 ) 2 Any one or a combination of at least two of the following;
preferably, the Cu salt comprises CuSO 4 、CuCl 2 Or Cu (NO) 3 ) 2 Any one or a combination of at least two of the following;
preferably, the Zn salt comprises ZnSO 4 、ZnCl 2 Or Zn (NO) 3 ) 2 Any one or a combination of at least two of them；
Preferably, the Mg salt comprises MgSO 4 、MgCl 2 Or Mg (NO) 3 ) 2 Any one or a combination of at least two of the following;
preferably, the Ti salt comprises Ti (SO 4 ) 2 、TiCl 4 Or TiO (acac) 2 Any one or a combination of at least two of the following;
preferably, the W salt comprises Na 2 WO 4 、(NH 4 ) 2 WO 2 Cl 4 、Na 2 WO 2 Cl 4 Any one or a combination of at least two of the following;
preferably, the Mo salt comprises Na 2 MoO 4 、(NH 4 ) 6 Mo 7 O 24 Or (NH) 4 ) 2 MoOCl 5 Any one or a combination of at least two of these.
5. The method according to any one of claims 2 to 4, wherein the carrier comprises any one of conductive glass, foamed nickel, carbon paper, carbon cloth, or woven nickel mesh.
6. The method of any one of claims 2 to 5, wherein the method of preparing the electrodeposition solution comprises:
mixing the metal salt with a solvent to obtain a primary mixed solution, mixing the primary mixed solution with a regulator and a stabilizer to obtain a remixed solution, and regulating the remixed solution to a set pH value by using acid and/or alkali to obtain the electrodeposition solution.
7. The method of preparation of claim 6, wherein the solvent comprises water;
preferably, the modifier comprises any one or a combination of at least two of boric acid, silicic acid or acetic acid;
preferably, the concentration of the regulator in the electrodeposition solution is 0.5-2 mol/L;
preferably, the stabilizer comprises any one or a combination of at least two of sodium citrate and/or potassium citrate;
preferably, the concentration of the stabilizer in the electrodeposition solution is 0.1 to 0.5mol/L;
preferably, the acid comprises any one or a combination of at least two of sulfuric acid, hydrochloric acid or nitric acid;
preferably, the base comprises any one or a combination of at least two of sodium hydroxide and/or potassium hydroxide;
preferably, the set pH is 2 to 10.
8. The method of any one of claims 2 to 7, wherein the electrodeposition comprises constant current electrodeposition, constant voltage electrodeposition, or pulsed voltage electrodeposition;
preferably, the electric potential of the electrodeposition is-0.6 to-2V for 100 to 7200s;
preferably, the pulse voltage electrodeposition is performed at an interval of 1 to 10 seconds.
9. The production method according to any one of claims 2 to 8, characterized in that the production method further comprises washing and drying performed sequentially after the electrodeposition;
preferably, the solution used for the washing comprises water and/or ethanol;
preferably, the drying method comprises infrared lamp irradiation or vacuum drying.
10. The production method according to any one of claims 2 to 9, characterized in that the production method comprises:
mixing the metal salt with water to obtain a primary mixed solution, mixing the primary mixed solution with a regulator with the concentration of 0.5-2 mol/L and a stabilizer with the concentration of 0.1-0.5 mol/L to obtain a remixed solution, and regulating the remixed solution to pH value of 2-10 by using acid and/or alkali to obtain the electrodeposition solution; placing any one of conductive glass, foam nickel, carbon paper, carbon cloth or woven nickel screen into an electrodeposition solution, performing electrodeposition for 100-7200 s at a potential of-0.6V to-2V, washing with water and/or ethanol, and drying by irradiation of an infrared lamp or vacuum drying to obtain the high-entropy alloy catalyst;
the electrodeposition solution includes a metal salt including any five of an Fe salt having a concentration of 0.01 to 0.5mol/L, a Ni salt having a concentration of 0.01 to 0.5mol/L, a Co salt having a concentration of 0.01 to 0.5mol/L, an Mn salt having a concentration of 0.01 to 0.5mol/L, a Cu salt having a concentration of 0.01 to 0.5mol/L, a Zn salt having a concentration of 0.01 to 0.5mol/L, a Mg salt having a concentration of 0.01 to 0.5mol/L, a Ti salt having a concentration of 0.01 to 0.5mol/L, a W salt having a concentration of 0.01 to 0.5mol/L, or a Mo salt having a concentration of 0.01 to 0.5mol/L, and a difference between the highest concentration and the lowest concentration of the five salts included in the electrodeposition solution is not higher than 0.3mol/L.
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