A multi-component alloy and a method for producing and using the same

Abstract

The application discloses a multi-element alloy and a preparation method and application thereof. The preparation method of the multi-element alloy comprises the following steps: a mixture of an absorbing material and a precursor is treated by laser. The preparation method can effectively reduce the preparation cost of the multi-element alloy, improve the preparation efficiency of the multi-element alloy, and has strong universality and is suitable for preparing various multi-element alloys. The application further provides the multi-element alloy prepared by the above preparation method and application of the obtained multi-element alloy.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of new materials, in particular to a multi-element alloy and a preparation method and application thereof. BACKGROUND

[0002] The multi-element alloy is an alloying material composed of two or more metals, which is usually used as a catalyst in the fields of batteries, organic synthesis, etc. Due to its unique microstructure, the multi-element alloy has multi-element effect, lattice distortion effect, hysteresis diffusion effect and "cocktail" effect, and thus has high catalytic activity and stability for various catalytic reactions. That is to say, the multi-element alloy-based catalyst has great application prospect in the field of catalysis, especially in the field of electrocatalysis.

[0003] However, the current synthesis method of the multi-element alloy-based catalyst is relatively complicated and time-consuming, and the size of the multi-element alloy-based catalyst is difficult to control, resulting in high cost of large-scale preparation. Therefore, it is urgent to develop an efficient and low-cost process to prepare multi-element. SUMMARY

[0004] The present application aims to at least solve one of the technical problems existing in the prior art. To this end, the present application provides a preparation method of a multi-element alloy, which can effectively reduce the preparation cost of the multi-element alloy, while improving the preparation efficiency, and the preparation method has strong universality and is suitable for preparing various multi-element alloys.

[0005] The present application also provides a multi-element alloy prepared by the above preparation method.

[0006] The present application also provides an application of the above multi-element alloy.

[0007] According to the embodiment of the first aspect of the present application, a preparation method of a multi-element alloy is provided, which comprises:

[0008] The mixture of the light-absorbing material and the precursor is treated by laser;

[0009] The light-absorbing material includes at least one of carbon-based material, molybdenum disulfide, tungsten disulfide, MXene, black phosphorus and two-dimensional selenium compound;

[0010] The precursor includes at least two of cobalt-based material, iron-based material, nickel-based material, copper-based material, manganese-based material, platinum-based material, palladium-based material, gold-based material, indium-based material, titanium-based material, silver-based material, ruthenium-based material, iridium-based material, chromium-based material, tin-based material, vanadium-based material, lanthanum-based material, cerium-based material, antimony-based material, tellurium-based material, bismuth-based material, niobium-based material, tungsten-based material and molybdenum-based material.

[0011] The preparation method according to the embodiment of the present application has at least the following beneficial effects:

[0012] (1) In the preparation process of the multi-element alloy, it is required to be quickly heated to a specified temperature, for example, quickly to 1500℃, to promote the cracking of the precursor, or to promote the reaction to generate the target product, and to promote the crystal type recombination of the target atoms in the precursor. In the traditional preparation method, the heating speed is slow, or the required temperature cannot be reached, so that the prepared multi-element alloy has poor performance, low generation efficiency and high cost.

[0013] In the preparation method provided by the present application, the light-absorbing material has the ability to absorb light energy and release high temperature. The combination of laser treatment and light-absorbing material can bring heating effect on one hand, and the light-absorbing material can reach high temperature (≥1500℃, even ≥2000℃) after absorbing the energy of the laser on the other hand. Thus, the problems in the traditional technology are overcome, and the performance of the obtained multi-element alloy and the preparation efficiency of the multi-element alloy are significantly improved.

[0014] (2) In the preparation method provided by the present application, the type, irradiation intensity and irradiation time of the laser in the laser treatment, and the type of the precursor, the ratio between the precursor and the light-absorbing material can be adjusted, and then the type, atomic ratio, particle size and crystal structure of the obtained multi-element alloy can be adjusted, so as to realize the functionalization of the multi-element alloy, improve the catalyst activity and stability, and broaden the application range of the obtained multi-element alloy.

[0015] (3) The preparation method provided by the present application can realize the controllable preparation of the multi-element alloy base by only combining the laser treatment and the light-absorbing material, which is simple to operate and easy to realize industrial large-scale production and application.

[0016] According to some embodiments of the present application, the mass ratio of the precursor to the light-absorbing material is 1:0.1-100. For example, it can be specifically 0.1-1 mass parts of the precursor matched with 0.1-10 mass parts of the light-absorbing material.

[0017] According to some embodiments of the present application, the mass ratio of the precursor to the light-absorbing material is 1:0.12-2. For example, it can be specifically about 1:0.4, 1:0.65, 1:0.195, 1:1.1, 1:0.12 or 1:1.

[0018] According to some embodiments of the present application, in the light-absorbing material, the carbon-based material includes at least one of graphene oxide, graphene, graphdiyne, carbon quantum dots, carbon black, graphite, carbon nanotubes, fullerene, carbon paper and carbon cloth. The graphene indicates unmodified graphene.

[0019] According to some embodiments of the present application, the MXene includes at least one of Ti3C2T x and V2CT x .

[0020] According to some embodiments of the present application, the light absorbing material comprises at least one of graphene oxide, molybdenum disulfide, carbon nanotube, Ti3C2T x

[0021] During the laser processing, the light absorbing material is at least one of kept as is, oxidized away, and reacted with the precursor. For example, when the light absorbing material is black phosphorus, the light absorbing material can act as a phosphorus source to cause the multi-component alloy to form a phosphide state.

[0022] According to some embodiments of the present application, the precursor comprises at least one of a single element and a compound of a target element, the target element being an element that forms the multi-component alloy.

[0023] According to some embodiments of the present application, the cobalt-based material comprises at least one of cobalt, cobalt sulfate, cobalt acetate, cobalt nitrate, cobalt acetylacetonate (CAS: 14024-48-7), and cobalt oxide (CoO).

[0024] According to some embodiments of the present application, the cobalt-based material comprises at least one of cobalt nitrate, cobalt sulfate, and cobalt acetate.

[0025] According to some embodiments of the present application, the iron-based material comprises at least one of iron, iron nitrate, iron sulfate, iron oxide, and citric acid iron (CAS: 17217-76-4 or CAS: 3522-50-7).

[0026] According to some embodiments of the present application, the iron-based material comprises iron nitrate.

[0027] According to some embodiments of the present application, the nickel-based material comprises at least one of nickel, nickel sulfate, nickel nitrate, nickel oxide, and nickel acetate.

[0028] According to some embodiments of the present application, the nickel-based material comprises at least one of nickel sulfate and nickel nitrate.

[0029] According to some embodiments of the present application, the copper-based material comprises at least one of copper, copper sulfate, cuprous oxide, copper nitrate, copper acetylacetonate, and copper acetate.

[0030] According to some embodiments of the present application, the copper-based material comprises at least one of copper sulfate and copper acetylacetonate.

[0031] According to some embodiments of the present application, the manganese-based material comprises at least one of manganese, manganese nitrate, manganese oxide, manganese acetylacetonate, and manganese carbonate.

[0032] According to some embodiments of the present application, the manganese-based material comprises at least one of manganese nitrate, manganese oxide, and manganese acetylacetonate. ​

[0033] According to some embodiments of the application, the platinum-based material comprises at least one of platinum, chloroplatinic acid, platinum oxide (CAS: 1314-15-4), and tetraammineplatinum chloride (CAS: 13820-46-7).

[0034] According to some embodiments of the application, the platinum-based material comprises chloroplatinic acid.

[0035] According to some embodiments of the application, the palladium-based material comprises at least one of palladium, palladium chloride, palladium hydroxide (CAS: 12135-22-7), and palladium oxide.

[0036] According to some embodiments of the application, the gold-based material comprises at least one of gold, gold oxide, potassium auric cyanide (CAS: 13967-50-5), potassium chloroaurate (CAS: 13682-61-6), and chloro(trimethylphosphine)gold (CAS: 15278-97-4).

[0037] According to some embodiments of the application, the indium-based material comprises at least one of indium chloride and indium sulfate.

[0038] According to some embodiments of the application, the gold-based material comprises chloroauric acid.

[0039] According to some embodiments of the application, the indium-based material comprises at least one of indium, indium oxide, indium hydroxide, indium chloride, indium nitrate, indium sulfide, indium sulfate, and indium monoidide (CAS: 13966-94-4).

[0040] According to some embodiments of the application, the titanium-based material comprises at least one of titanium, titanium n-propoxide, titanium tetrachloride, titanate, hexafluorotitanic acid, ammonium fluorotitanate, titanium iso-octoxide, potassium titanium oxalate, calcium titanate, and cyclopentadienyl titanium trichloride (CAS: 1270-98-0).

[0041] According to some embodiments of the application, the titanium-based material comprises cyclopentadienyl titanium trichloride.

[0042] According to some embodiments of the application, the silver-based material comprises at least one of silver, silver chloride, silver nitrate, silver oxide, silver tetrafluoroborate (CAS: 14104-20-2), silver cyanide (CAS: 506-64-9), silver iodate, silver citrate, silver acetate, silver phosphate, silver acetylacetonate (CAS: 15525-64-1), and silver perchlorate (CAS: 7783-93-9).

[0043] According to some embodiments of the application, the silver-based material comprises silver nitrate.

[0044] According to some embodiments of the application, the ruthenium-based material comprises at least one of ruthenium, ruthenium oxide, ruthenium acetate, ruthenium acetylacetonate, ruthenium nitrate, ruthenium trichloride and ruthenium sulfide.

[0045] According to some embodiments of the application, the ruthenium-based material comprises at least one of ruthenium trichloride and ruthenium sulfide.

[0046] According to some embodiments of the application, the iridium-based material comprises at least one of iridium, iridium oxide, iridium chloride, iridium acetylacetonate, ammonium chloroiridate (CAS: 16940-92-4), iridium bromide, tetrakis(acetonitrile)iridium (CAS: 11065-24-0) and potassium hexachloroiridate (CAS: 14024-41-0 or CAS: 16920-56-2).

[0047] According to some embodiments of the application, the iridium-based material comprises iridium oxide.

[0048] According to some embodiments of the application, the chromium-based material comprises at least one of chromium, chromium acetate, sodium chromate, chromium chloride, chromium sulfate, zinc chromate, strontium chromate, ammonium chromate and cobalt chromate (CAS: 12016-69-2).

[0049] According to some embodiments of the application, the chromium-based material comprises zinc chromate.

[0050] According to some embodiments of the application, the tin-based material comprises at least one of tin, tin dioxide, sodium stannate, tin iodide, butyl stannoic acid (CAS: 2273-43-0), stannous oxalate, tin tetrachloride (CAS: 7646-78-8) and tributyl tin oxide.

[0051] According to some embodiments of the application, the tin-based material comprises tributyl tin oxide.

[0052] According to some embodiments of the application, the vanadium-based material comprises at least one of vanadium, vanadium chloride, sodium orthovanadate, vanadium acetylacetonate, sodium metavanadate, vanadium fluoride (CAS: 10049-12-4), vanadium oxide and bis(cyclopentadienyl)vanadium (CAS: 1277-47-0).

[0053] According to some embodiments of the application, the vanadium-based material comprises sodium vanadate.

[0054] According to some embodiments of the application, the lanthanum-based material comprises at least one of lanthanum, lanthanum chloride, lanthanum nitrate, lanthanum acetate, lanthanum acetylacetonate, lanthanum carbonate, lanthanum hydroxide, lanthanum borate (CAS: 13709-95-0), lanthanum sulfate and lanthanum nickelate hexahydrate (CAS: 10277-43-7).

[0055] According to some embodiments of the application, the lanthanum-based material comprises lanthanum nitrate.

[0056] According to some embodiments of the application, the cerium-based material comprises at least one of cerium, cerium oxide, cerium nitrate, cerium chloride, cerium bromide, cerium perchlorate, cerium oxalate and cerium bis(trifluoromethylsulfonyl)imide (CAS: 1046099-39-1).

[0057] According to some embodiments of the application, the cerium-based material comprises cerium bis(trifluoromethylsulfonyl)imide.

[0058] According to some embodiments of the application, the antimony-based material comprises at least one of antimony, antimony acetate, antimony iodide (CAS: 7790-44-5), antimony fluoride (CAS: 16950-06-4, also known as fluoroantimonic acid), sodium antimony tartrate, triethylantimony, antimony oxide, antimony hexafluoride nitrate (CAS: 17856-92-7) and tetraphenylantimony bromide.

[0059] According to some embodiments of the application, the antimony-based material comprises antimony fluoride.

[0060] According to some embodiments of the application, the tellurium-based material comprises at least one of tellurium, lead telluride, cadmium telluride and tellurium tetrachloride.

[0061] According to some embodiments of the application, the tellurium-based material comprises tellurium.

[0062] According to some embodiments of the application, the bismuth-based material comprises bismuth chloride (CAS: 7787-60-2).

[0063] According to some embodiments of the application, the niobium-based material comprises niobium oxide (CAS: 1313-96-8).

[0064] According to some embodiments of the application, the tungsten-based material comprises at least one of tungsten, tungsten disulfide (IV) (CAS: 182482-83-3), tungsten sulfide (CAS: 12138-09-9), tungsten oxide, tungstic acid, tungsten chloride (CAS: 13283-01-7), sodium tungstate, tungsten titanium (CAS: 58397-70-9), cobalt tungstate (CAS: 12640-47-0) and bismuth tungsten oxide (CAS: 13595-87-4).

[0065] According to some embodiments of the application, the tungsten-based material comprises at least one of cobalt tungstate and sodium tungstate.

[0066] According to some embodiments of the application, the molybdenum-based material comprises at least one of molybdenum, molybdenum oxide, molybdenum disulfide, sodium molybdate, molybdenum selenide, molybdenum chloride, molybdenum nitrate and tris(N-tert-butyl-3,5-dimethylbenzenaminyl) molybdenum (CAS: 236740-70-8).

[0067] According to some embodiments of the application, the molybdenum-based material comprises at least one of sodium molybdate and molybdenum oxide.

[0068] According to some embodiments of the application, the precursor comprises at least two of a cobalt-based material, an iron-based material, a nickel-based material, a copper-based material, a manganese-based material, a platinum-based material, a gold-based material, an indium-based material, a titanium-based material, a silver-based material, a ruthenium-based material, an iridium-based material, a chromium-based material, a tin-based material, a vanadium-based material, a lanthanum-based material, a cerium-based material, an antimony-based material, a tellurium-based material, a bismuth-based material, a niobium-based material, a tungsten-based material and a molybdenum-based material.

[0069] By using laser treatment, the compatibility between the target elements in the resulting multi-element alloy can be significantly improved, and the preparation steps can be simplified.

[0070] According to some embodiments of the application, the precursor consists of a nickel-based material, a manganese-based material, an iron-based material, a cobalt-based material and a platinum-based material.

[0071] In this composition, the mass ratio of the nickel-based material and the manganese-based material is 10:1-3, and can be specifically about 5:1;

[0072] The mass ratio of the nickel-based material and the iron-based material is 10:1-3, and can be specifically about 5:1;

[0073] The mass ratio of the nickel-based material and the cobalt-based material is 10:1-3, and can be specifically about 5:1;

[0074] The mass ratio of the nickel-based material and the platinum-based material is 10:1-3, and can be specifically about 5:1;

[0075] The nickel-based material comprises nickel nitrate;

[0076] The manganese-based material comprises manganese nitrate;

[0077] The iron-based material comprises iron nitrate;

[0078] The cobalt-based material comprises cobalt nitrate;

[0079] The platinum-based material comprises chloroplatinic acid;

[0080] The resulting multi-element alloy comprises the elements nickel, manganese, iron, cobalt and platinum.

[0081] According to some embodiments of the application, the precursor consists of a copper-based material, a manganese-based material, a bismuth-based material, an indium-based material and a titanium-based material.

[0082] In this composition, the mass ratio of the copper-based material and the manganese-based material is 5:1.5-2.5, and can be specifically about 5:2;

[0083] The mass ratio of the copper-based material and the bismuth-based material is 5:1.5-2.5, and for example can be about 5:2;

[0084] The mass ratio of the copper-based material and the indium-based material is 5:0.8-1.2, and for example can be about 5:1;

[0085] The mass ratio of the copper-based material and the titanium-based material is 5:1.5-2.5, and for example can be about 5:2;

[0086] The copper-based material includes copper sulfate;

[0087] The manganese-based material includes manganese acetylacetonate;

[0088] The bismuth-based material includes bismuth chloride;

[0089] The indium-based material includes indium sulfate;

[0090] The titanium-based material includes cyclopentadienyl titanium trichloride.

[0091] Thus, the resulting multi-element alloy contains the elements copper, manganese, bismuth, indium and titanium.

[0092] According to some embodiments of the application, the precursor is composed of a molybdenum-based material, a chromium-based material, a ruthenium-based material, an iridium-based material, a tungsten-based material and a tin-based material.

[0093] In this composition, the mass ratio of the molybdenum-based material and the chromium-based material is 2:1.5-2.5, and for example can be about 1:1;

[0094] The mass ratio of the molybdenum-based material and the ruthenium-based material is 2:1.5-2.5, and for example can be about 1:1;

[0095] The mass ratio of the molybdenum-based material and the iridium-based material is 2:0.8-1.2, and for example can be about 2:1;

[0096] The mass ratio of the molybdenum-based material and the tungsten-based material is 2:0.8-1.2, and for example can be about 2:1;

[0097] The mass ratio of the molybdenum-based material and the tin-based material is 2:1.5-2.5, and for example can be about 1:1;

[0098] The molybdenum-based material includes sodium molybdate;

[0099] The chromium-based material includes zinc chromate;

[0100] The ruthenium-based material includes ruthenium trichloride;

[0101] The iridium-based material includes iridium oxide;

[0102] The tungsten-based material includes cobalt tungstate;

[0103] The tin-based material comprises tributyltin oxide.

[0104] The resulting multi-element alloy material comprises the elements molybdenum, chromium, ruthenium, iridium, tungsten and tin, and possibly cobalt and zinc.

[0105] According to some embodiments of the application, the precursor consists of a vanadium-based material, a manganese-based material, a cobalt-based material, a ruthenium-based material, a lanthanum-based material, a silver-based material, a gold-based material and an antimony-based material.

[0106] The mass ratio of the vanadium-based material and the manganese-based material in this composition is 5:4.5-5.5, and can specifically be about 1:1;

[0107] The mass ratio of the vanadium-based material and the cobalt-based material is 5:4.5-5.5, and can specifically be about 1:1;

[0108] The mass ratio of the vanadium-based material and the ruthenium-based material is 5:0.8-1.2, and can specifically be about 5:1;

[0109] The mass ratio of the vanadium-based material and the lanthanum-based material is 5:0.8-1.2, and can specifically be about 5:1;

[0110] The mass ratio of the vanadium-based material and the silver-based material is 5:0.8-1.2, and can specifically be about 5:1;

[0111] The mass ratio of the vanadium-based material and the gold-based material is 5:0.8-1.2, and can specifically be about 5:1;

[0112] The mass ratio of the vanadium-based material and the antimony-based material is 5:0.4-0.6, and can specifically be about 10:1;

[0113] The vanadium-based material comprises sodium metavanadate;

[0114] The manganese-based material comprises manganese oxide;

[0115] The cobalt-based material comprises cobalt sulfate;

[0116] The ruthenium-based material comprises ruthenium sulfide;

[0117] The lanthanum-based material comprises lanthanum nitrate;

[0118] The silver-based material comprises silver nitrate;

[0119] The gold-based material comprises chloroauric acid;

[0120] The antimony-based material comprises antimony fluoride;

[0121] The resulting multi-element alloy thus comprises the elements vanadium, manganese, cobalt, ruthenium, lanthanum, silver, gold and antimony.

[0122] According to some embodiments of the application, the precursor is composed of a copper-based material, a silver-based material, a cerium-based material, a molybdenum-based material, a niobium-based material, a tungsten-based material, an indium-based material and a tellurium-based material.

[0123] In this composition, the mass ratio of the copper-based material and the silver-based material is 10:8-12, for example, specifically, it can be about 1:1;

[0124] The mass ratio of the copper-based material and the cerium-based material is 10:4-6, for example, specifically, it can be about 2:1;

[0125] The mass ratio of the copper-based material and the molybdenum-based material is 10:8-12, for example, specifically, it can be about 1:1;

[0126] The mass ratio of the copper-based material and the niobium-based material is 10:8-12, for example, specifically, it can be about 1:1;

[0127] The mass ratio of the copper-based material and the tungsten-based material is 10:8-12, for example, specifically, it can be about 1:1;

[0128] The mass ratio of the copper-based material and the indium-based material is 10:4-6, for example, specifically, it can be about 2:1;

[0129] The mass ratio of the copper-based material and the tellurium-based material is 10:4-6, for example, specifically, it can be about 2:1;

[0130] The copper-based material includes copper acetylacetonate;

[0131] The silver-based material includes silver nitrate;

[0132] The cerium-based material includes bis(trifluoromethanesulfonyl) imide cerium;

[0133] The molybdenum-based material includes molybdenum oxide;

[0134] The niobium-based material includes niobium oxide;

[0135] The tungsten-based material includes sodium tungstate;

[0136] The indium-based material includes indium chloride;

[0137] The tellurium-based material includes tellurium (elemental).

[0138] Thus, the resulting multi-element alloy includes the elements copper, silver, cerium, molybdenum, niobium, tungsten, indium and tellurium.

[0139] According to some embodiments of the application, the precursor is composed of a nickel-based material and a cobalt-based material.

[0140] In this composition, the mass ratio of the nickel-based material and the cobalt-based material is 2:1-3, for example, specifically, it can be about 1:1.

[0141] The nickel-based material includes nickel sulfate;

[0142] The cobalt-based material includes cobalt acetate.

[0143] Thus, the obtained multi-element alloy includes elements nickel and cobalt.

[0144] According to some embodiments of the present application, the mixture further includes an element additive, which includes at least one of a nitrogen source, a phosphorus source and a sulfur source.

[0145] Thus, the target elements in the precursor can react with the element additive, and the final obtained multi-element alloy can contain at least one of sulfides, nitrides and phosphides of the target elements.

[0146] According to some embodiments of the present application, the mass ratio of the element additive to the precursor is 1:0.3-0.5, for example, specifically about 1:0.4.

[0147] According to some embodiments of the present application, the nitrogen source includes at least one of urea, thiourea, melamine, dicyandiamide, monocyandiamide and g-C3N4(graphite-like phase carbon nitride).

[0148] According to some embodiments of the present application, the phosphorus source includes at least one of sodium phosphate, ammonium phosphate, sodium hydrogen phosphate, phosphorus pentoxide and elemental phosphorus.

[0149] According to some embodiments of the present application, the sulfur source includes at least one of thioacetamide, sodium sulfide, thiourea, hydrogen sulfide, ammonium thiosulfate and elemental sulfur.

[0150] According to some embodiments of the present application, the sulfur source includes thioacetamide.

[0151] According to some embodiments of the present application, the method for obtaining the mixture includes at least one of dry mixing and wet mixing. Thus, the precursors are uniformly mixed with each other, and the precursors are uniformly loaded on the light-absorbing material to form close contact, so that the obtained multi-element alloy has uniform particle size distribution.

[0152] According to some embodiments of the present application, the wet mixing includes mixing the substances to be mixed in a solvent and removing the solvent.

[0153] According to some embodiments of the present application, the solvent includes at least one of water, acetonitrile, ethanol, acetone, heptane, toluene, chlorobenzene, dichloromethane, isopropyl alcohol, ethyl acetate, dimethyl sulfoxide, butanedione, dimethyl formamide and acetamide.

[0154] According to some embodiments of the present application, the method of obtaining the mixture is selected from dry mixing; further, the method of dry mixing comprises at least one of stirring and grinding.

[0155] According to some embodiments of the present application, the atmosphere of the laser treatment comprises one of an oxidizing atmosphere, a reducing atmosphere, a corrosive atmosphere and a chemically inert atmosphere.

[0156] wherein the oxidizing atmosphere causes the resulting multi-component alloy to have oxidized substances; the reducing atmosphere causes the resulting multi-component alloy to have elemental substances; in the chemically inert atmosphere, the resulting multi-component alloy is in an elemental state, or a state resulting from a reaction with the elemental additives. The corrosive atmosphere can regulate surface defects of the multi-component alloy.

[0157] According to some embodiments of the present application, the oxidizing atmosphere comprises at least one of oxygen and air.

[0158] According to some embodiments of the present application, the reducing atmosphere comprises at least one of carbon monoxide, hydrogen, ammonia, methane and ethane.

[0159] According to some embodiments of the present application, the chemically inert atmosphere comprises at least one of nitrogen, neon, argon, carbon dioxide and helium.

[0160] According to some embodiments of the present application, the corrosive atmosphere comprises at least one of chlorine, hydrogen fluoride and hydrogen chloride.

[0161] According to some embodiments of the present application, the atmosphere of the laser treatment comprises at least one of oxygen and argon.

[0162] According to some embodiments of the present application, in the laser treatment, the power of the laser is 100 milliwatts to 2000 watts. For example, it can be about 10 watts, 50 watts, 100 watts, 200 watts, 500 watts, 1000 watts or 1500 watts.

[0163] According to some embodiments of the present application, in the laser treatment, the irradiation time is between 100 ms and 1 h. For example, it can be 3 min, 6 min, 12 min, 30 min or 42 min.

[0164] The nucleation rate, crystal face orientation and particle size of the multi-component alloy can be reasonably adjusted by adjusting the power and irradiation time of the laser, so as to adjust the catalytic activity of the obtained multi-component alloy catalyst. Within the above power and time range, the temperature and temperature rising rate generated by the light-absorbing material can generate a multi-component alloy, and the performance of the multi-component alloy is more excellent; in addition, the nucleation and growth rate of the multi-component alloy during preparation is moderate, and the particle size and distribution of the finally obtained multi-component alloy are more excellent, and there is basically no agglomeration phenomenon, and the specific surface area, catalytic activity and stability when used as a catalyst are very excellent.

[0165] According to some embodiments of the present application, the laser used in the laser treatment is at least one of far-infrared laser, mid-infrared laser, near-infrared laser, visible laser, near-ultraviolet laser and carbon dioxide laser. In the present application, the type of laser is not strictly limited, as long as it can meet the corresponding power and produce strong action with the light-absorbing material to quickly generate high temperature. In actual production, the type of laser can also be adjusted according to the existing conditions.

[0166] The wavelength range of the far-infrared laser is 50-1000 μm;

[0167] The wavelength range of the mid-infrared laser is 3-8 μm;

[0168] The wavelength range of the near-infrared laser is 0.75-1.4 μm;

[0169] The wavelength range of the visible laser is 360-400 nm;

[0170] The wavelength range of the near-ultraviolet laser is 200-380 nm.

[0171] According to the embodiments of the second aspect of the present application, a multi-component alloy prepared by the preparation method is provided.

[0172] Since the multi-component alloy adopts all the technical solutions of the preparation method of the above embodiments, it at least has all the beneficial effects brought by the technical solutions of the above embodiments.

[0173] In addition, due to the mutual coordination between the preparation process and the raw materials, the atomic arrangement and exposed active crystal face of the multi-component alloy provided by the present application are controllable, and the multi-component alloy has high catalytic activity and stability.

[0174] Most importantly, the multi-component alloy provided by the present application combines the intrinsic catalytic activity of a variety of metals (non-metals), and fully exposes the high catalytic crystal face, thereby having high catalytic activity and stability.

[0175] According to some embodiments of the present application, the multi-element alloy refers to an alloy with the number of target elements ≥2, for example, a binary alloy, a quaternary alloy, a quinary alloy, a sexinary alloy, a septenary alloy or an octenary alloy.

[0176] According to some embodiments of the present application, the mass percentage of the metal elements in the multi-element alloy is between 0.5% and 21%.

[0177] According to some embodiments of the present application, the mass percentage of the metal elements in the multi-element alloy is between 2 and 18.8%. For example, it can be about 2.05%, 3.9%, 10.2%, 12.1%, 18.75% or 20.9%.

[0178] According to some embodiments of the present application, the multi-element alloy includes at least one of an element, an oxide, a sulfide, a nitride and a phosphide.

[0179] According to some embodiments of the present application, the multi-element alloy is a nickel-manganese-iron-cobalt-platinum oxide. Thus, the multi-element alloy can be used to prepare a zinc-air battery (positive electrode), and has high catalytic activity and stability.

[0180] The mass ratio of nickel to manganese is 1:0.9-1.1. The mass ratio of nickel to iron is 1:0.9-1.1. The mass ratio of nickel to cobalt is 1:0.5-0.8. The mass ratio of nickel to platinum is 1:1-1.2. In the multi-element alloy, the sum of the mass percentages of the elements nickel, manganese, iron, cobalt and platinum is between 3.5 and 4%.

[0181] According to some embodiments of the present application, the multi-element alloy is a copper-manganese-bismuth-indium-titanium alloy (elemental state). Thus, the multi-element alloy can be used in the organic process of catalyzing the reduction of carbon dioxide to prepare ethanol, and has high catalytic activity and stability.

[0182] The mass ratio of copper to manganese is 4:1.5-2. The mass ratio of copper to bismuth is 4:1.5-1.8. The mass ratio of copper to indium is 4:0.5-0.8. The mass ratio of copper to titanium is 4:1.9-2.1. In the multi-element alloy, the sum of the mass percentages of the elements copper, manganese, bismuth, indium and titanium is between 10 and 10.5%.

[0183] According to some embodiments of the present application, the multi-element alloy is a molybdenum-chromium-ruthenium-iridium-tungsten-tin alloy (elemental state). Thus, the multi-element alloy can be used to catalyze the overall water splitting, and has high catalytic activity and stability.

[0184] The mass ratio of molybdenum and chromium is 1:0.9-1. The mass ratio of molybdenum and ruthenium is 1:9-10. The mass ratio of molybdenum and iridium is 1:5-6. The mass ratio of molybdenum and tungsten is 1:5-6. The mass ratio of molybdenum and tin is 1:0.5-0.6. In the multi-element alloy, the sum of the mass percentages of molybdenum, chromium, ruthenium, iridium, tungsten and tin is between 20-21%.

[0185] According to some embodiments of the present application, the multi-element alloy is vanadium-manganese-cobalt-ruthenium-lanthanum-silver-gold-antimony alloy (single element state). Thus, the multi-element alloy can be used to prepare lithium-carbon dioxide batteries and has high catalytic activity and stability.

[0186] The mass ratio of vanadium and manganese is 1:0.9-1.1. The mass ratio of vanadium and cobalt is 1:0.9-1.1. The mass ratio of vanadium and ruthenium is 1:0.2-0.25. The mass ratio of vanadium and lanthanum is 1:0.15-0.2. The mass ratio of vanadium and silver is 1:0.15-0.2. The mass ratio of vanadium and gold is 1:0.15-0.2. The mass ratio of vanadium and antimony is 1:0.2-0.21. In the multi-element alloy, the sum of the mass percentages of vanadium, manganese, cobalt, ruthenium, lanthanum, silver, gold and antimony is between 18.5-19%.

[0187] According to some embodiments of the present application, the multi-element alloy is copper-silver-cerium-molybdenum-niobium-tungsten-indium-tellurium phosphide. Thus, the multi-element alloy can be used in the catalytic nitrogen reduction process to prepare ammonia and has high catalytic activity and stability.

[0188] The mass ratio of copper and silver is 1:0.85-0.86. The mass ratio of copper and cerium is 1:0.35-0.4. The mass ratio of copper and molybdenum is 1:1-1.1. The mass ratio of copper and niobium is 1:1-1.1. The mass ratio of copper and tungsten is 1:1-1.1. The mass ratio of copper and indium is 1:0.35-0.4. The mass ratio of copper and tellurium is 1:0.3-0.35. In the multi-element alloy, the sum of the mass percentages of copper, silver, cerium, molybdenum, niobium, tungsten, indium and tellurium is between 12-13%, and the sum of the mass percentages of other elements except tellurium is between 11.8-12.5%.

[0189] According to some embodiments of the present application, the multi-element alloy is nickel-cobalt sulfide. Thus, the multi-element alloy can be used to prepare lithium-oxygen batteries and has high catalytic activity and stability.

[0190] The mass ratio of nickel and cobalt is 1:0.85-0.9. In the multi-element alloy, the sum of the mass percentages of nickel and cobalt is 2-2.1%.

[0191] According to embodiments of the third aspect of the present application, a catalyst is provided, and the raw material for preparing the catalyst comprises the multi-element alloy.

[0192] Since the catalyst adopts all the technical solutions of the multi-component alloy in the above embodiments, it has at least all the beneficial effects brought by the technical solutions of the above embodiments, that is, it can be catalyzed in multiple fields, and has high catalytic activity and high stability.

[0193] According to the embodiments of the fourth aspect of the present application, the multi-component alloy or the catalyst is applied in the field of batteries, the field of overall water splitting, and the field of organic synthesis.

[0194] Since the application adopts all the technical solutions of the multi-component alloy or the catalyst in the above embodiments, it has at least all the beneficial effects brought by the technical solutions of the above embodiments.

[0195] According to some embodiments of the present application, the field of batteries includes at least one of zinc-air batteries, lithium-carbon dioxide batteries, and lithium-oxygen batteries.

[0196] According to some embodiments of the present application, the field of organic synthesis includes at least one of catalytic preparation of ammonia from nitrogen and preparation of ethanol from carbon dioxide reduction.

[0197] Unless otherwise specified, "about" in the present application actually means that the allowed error is within ±2%, for example, about 100 actually means 100±2%*100.

[0198] Unless otherwise specified, "between" in the present application includes the numbers, for example, "between 2-3" includes the end values 2 and 3.

[0199] Other features and advantages of the present application will be set forth in the following description, and in part will become apparent from the description, or will be learned by practice of the present application. BRIEF DESCRIPTION OF DRAWINGS

[0200] The above and / or additional aspects and advantages of the present application will become apparent and be readily understood from the following description, taken in conjunction with the accompanying drawings, in which:

[0201] Figure 1 is a structural schematic diagram of an instrument used in embodiments of the present application.

[0202] Figure 2 is a scanning electron microscope image of the multi-component alloy obtained in Example 1 of the present application.

[0203] Figure 3 is a scanning electron microscope image of the multi-component alloy obtained in Example 2 of the present application.

[0204] Figure 4 is a scanning electron microscope image of the multi-component alloy obtained in Example 3 of the present application.

[0205] Figure 5is a scanning electron microscope image of the multi-element alloy obtained in Example 4 of the present application.

[0206] Figure 6 is a scanning electron microscope image of the multi-element alloy obtained in Example 5 of the present application.

[0207] Figure 7 is a scanning electron microscope image of the multi-element alloy obtained in Example 6 of the present application.

[0208] Reference numerals:

[0209] laser 100, laser 110;

[0210] reaction cavity 200, gas outlet 210, gas inlet 220;

[0211] reactant 300. DETAILED DESCRIPTION

[0212] Embodiments of the present application are described in detail below with reference to the attached drawing figures, wherein the same or like reference numerals and characters indicate the same or like components throughout the drawings. The embodiments described below are exemplary, and are merely intended to explain the present application, and are not to be interpreted as limiting the present application.

[0213] In the description of the present application, if there is a description to first, second, etc., it is only for the purpose of distinguishing technical features, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features or the sequence of indicated technical features.

[0214] In the description of the present application, it should be understood that the orientation description, such as up, down, etc., is based on the orientation or positional relationship shown in the drawings, and is only for the convenience of describing the present application and simplifying the description, and therefore cannot be understood as indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as limiting the present application.

[0215] In the description of the present application, it should be noted that, unless otherwise explicitly limited, the words such as setting, installing, connecting, etc. should be broadly understood, and the person skilled in the art can reasonably determine the specific meaning of the above words in the present application in combination with the specific content of the technical solution.

[0216] Unless otherwise specified, the specific embodiments all use the same as Figure 1The instrument shown, wherein the instrument comprises a reaction cavity 200 containing reactants 300 (light-absorbing material and precursor), the reaction cavity 200 is provided with an outlet 210 and an inlet 220, so that by adjusting the gas introduced into the inlet 220, different gas environments can be created for the reaction process. The instrument also includes a laser 100 that can emit a laser 110, thereby providing driving energy for the reaction process.

[0217] Example 1

[0218] In this embodiment, a multi-element alloy of nickel-manganese-iron-cobalt-platinum oxide is prepared, and the steps of the preparation method are as follows:

[0219] S1. 10 mg of graphene oxide (light-absorbing material, Shenzhen Encai Technology Co., Ltd., GO-1) is mixed with 2 mg of nickel nitrate, 2 mg of manganese nitrate, 2 mg of iron nitrate, 2 mg of cobalt nitrate and 2 mg of chloroplatinic acid by grinding;

[0220] S2. The mixture obtained in step S1 (reactants 300) is placed in the reaction cavity 200, and a mixed gas of oxygen and argon is introduced from the inlet 220, wherein the volume percentage of oxygen is 5%, and the excess gas is discharged from the outlet 210;

[0221] A visible laser 100 with a power of 100 milliwatts is used to emit a laser 110, and the surface of the mixture is irradiated for 0.2 h.

[0222] Example 2

[0223] In this embodiment, a multi-element alloy of copper-manganese-bismuth-indium-titanium is prepared, and the steps of the preparation method are as follows:

[0224] S1. 10 kg of molybdenum disulfide (light-absorbing material, Jiangsu Xianfeng Nanotechnology Co., Ltd., XF184-2) is mixed with 500 g of copper sulfate, 200 g of manganese acetylacetone, 200 g of bismuth chloride, 100 g of indium sulfate and 200 g of cyclopentadienyl titanium trichloride by grinding;

[0225] S2. The mixture obtained in step S1 (reactants 300) is placed in the reaction cavity 200; and an argon protective atmosphere is created in the reaction cavity 200.

[0226] An ultraviolet laser 100 with a power of 1000 watts is used to emit a laser 110, and the surface of the mixture is irradiated for 1 h.

[0227] Example 3

[0228] In this embodiment, a multi-element alloy of molybdenum-chromium-ruthenium-iridium-tungsten-tin is prepared, and the steps of the preparation method are as follows:

[0229] S1. 1 kg of carbon nanotubes (light-absorbing material, Jiangsu Xianfeng Nanometer Technology Co., Ltd., XFM01) was stirred and mixed with 200 g of sodium molybdate, 200 g of zinc chromate, 200 g of ruthenium trichloride, 100 g of iridium oxide, 100 g of cobalt tungstate, and 200 g of tributyltin oxide;

[0230] S2. The mixture obtained in step S1 (reactant 300) was placed in the reaction cavity 200; and an argon protective atmosphere was created in the reaction cavity 200.

[0231] A carbon dioxide laser 100 with a power of 1000 watts was used to emit laser light 110, and the surface of the mixture was irradiated for 1 h, and the product was obtained.

[0232] Example 4

[0233] In this example, a vanadium-manganese-cobalt-ruthenium-lanthanum-silver-gold-antimony multi-element alloy was prepared, and the steps of the preparation method were as follows:

[0234] S1. 10 kg of Ti3C2T x (MXene, light-absorbing material, Beijing Sanchuan Eneng Technology Co., Ltd., MXT-01) was ground and mixed with 500 g of sodium metavanadate, 500 g of manganese oxide, 500 g of cobalt sulfate, 100 g of ruthenium sulfide, 100 g of lanthanum nitrate, 100 g of silver nitrate, 100 g of chloroauric acid, and 50 g of antimony fluoride;

[0235] S2. The mixture obtained in step S1 (reactant 300) was placed in the reaction cavity 200; and an argon protective atmosphere was created in the reaction cavity 200.

[0236] A near-infrared laser 100 with a power of 500 watts was used to emit laser light 110, and the surface of the mixture was irradiated for 0.5 h, and the product was obtained.

[0237] Example 5

[0238] In this example, a copper-silver-cerium-molybdenum-niobium-tungsten-indium-tellurium phosphide multi-element alloy was prepared, and the steps of the preparation method were as follows:

[0239] S1. 100 g of black phosphorus (light-absorbing material, Jiangsu Xianfeng Nanometer Technology Co., Ltd., XF175) was stirred and mixed with 10 g of copper acetylacetonate, 10 g of silver nitrate, 5 g of bis(trifluoromethylsulfonyl) imidazole cerium, 10 g of molybdenum oxide, 10 g of niobium oxide, 10 g of sodium tungstate, 5 g of indium chloride, and 5 g of tellurium;

[0240] S2. The mixture obtained in step S1 (reactant 300) was placed in the reaction cavity 200; and an argon protective atmosphere was created in the reaction cavity 200.

[0241] A far-infrared laser 100 with a power of 100 watts emits laser light 110, and irradiates the surface of the mixture for 0.2 hours, to obtain the product.

[0242] Example 6

[0243] In this example, a nickel-cobalt sulfide multi-element alloy is prepared, and the steps of the preparation method are as follows:

[0244] S1. 10 g of graphdiyne (absorbing material, Jiangsu Xianfeng Nanometer Technology Co., Ltd., XFY01) is stirred and mixed with 2 g of nickel nitrate, 2 g of cobalt acetate, and 10 g of thioacetamide;

[0245] S2. The mixture (reactant 300) obtained in step S1 is placed in a reaction cavity 200, and an argon protective atmosphere is created in the reaction cavity 200.

[0246] A visible laser 100 with a power of 50 watts emits laser light 110, and irradiates the surface of the mixture for 0.05 hours, to obtain the product.

[0247] Comparative Example 1

[0248] In this comparative example, a nickel-manganese-iron-cobalt-platinum oxide multi-element alloy is prepared, and the difference between the preparation method and Example 1 is that:

[0249] In step S2, the mixture obtained in step S1 is placed in a high-temperature tube furnace, and a mixed atmosphere of argon and oxygen is used, with the volume percentage of oxygen being 5%, and the high temperature is set to 1200°C, and the heating reaction time is 20 hours, to obtain the product.

[0250] Application Example

[0251] In this application example, the multi-element alloys obtained in Examples 1-6 are used as catalysts, and their catalytic properties are tested, and the specific test conditions and test results are shown in Table 1.

[0252] Table 1 Test method and test results of the catalytic properties of the multi-element alloys obtained in Examples 1-6

[0253]

[0254]

[0255] In Table 1, the calculation of the Faraday efficiency is based on the theoretical consumption of electricity for the production of the product obtained by the chemical reaction divided by the actual consumption of electricity for the entire reaction.

[0256] From the results in Table 1, it can be seen that the multi-element alloy prepared by the present application has high catalytic activity and strong stability. Most importantly, the preparation method provided by the present application can prepare catalysts with different catalytic functions, and has strong universality.

[0257] Test Example

[0258] The test example first tests the mass percentage of the target elements in the obtained multi-element alloy, and the test method is ICP-OES. The test results are shown in Table 2.

[0259] Table 2 Partial composition of the multi-element alloy obtained in Examples 1-6

[0260] Mass ratio (wt%) Example 1 Nickel: Manganese: Iron: Cobalt: Platinum = 1 : 0.9 : 1.1 : 0.7 : 1.2 Example 2 Copper: Manganese: Bismuth: Indium: Titanium = 4 : 1.9 : 1.6 : 0.7 : 2 Example 3 Molybdenum: Chromium: Ruthenium: Iridium: Tungsten: Tin = 0.9 : 0.9 : 8.8 : 4.8 : 5 : 0.5 Example 4 Vanadium: Manganese: Cobalt: Ruthenium: Lanthanum: Silver: Gold: Antimony = 4.8 : 4.5 : 4.9 : 1.1 : 0.9 : 0.8 : 0.75 : 1 Example 5 Copper: Silver: Cerium: Molybdenum: Niobium: Tungsten: Indium: Tellurium = 2.1 : 1.8 : 0.8 : 2.2 : 2.1 : 2.3 : 0.8 : 0.7 Example 6 Nickel: Cobalt = 1.1 : 0.95

[0261] According to the test results in Table 2, the content of each element in the obtained product according to the preparation method provided by the present application is basically consistent with the preset value.

[0262] The test example also tests the appearance of the multi-element alloy obtained in Examples 1-6, and the test method is high-angle annular dark field scanning transmission electron microscopy. The test results show that the multi-element alloy prepared by the present application includes light-absorbing materials and particles (including physical loading) loaded on the surface of the light-absorbing materials, the particles are the reaction products of the precursors, the particle size is uniform, there is no agglomeration, and the particle size will change to a certain extent according to the conditions. Specifically, the particles in Example 1 are metal oxides, and the average particle size is about 200 nm; the particles in Example 2 are mainly elemental alloys, and the average particle size is about 50 nm; the particles in Example 3 are mainly elemental alloys, and the average particle size is about 150 nm; the particles in Example 4 are mainly elemental alloys, and the average particle size is about 30 nm; the particles in Example 5 are phosphides, and the particle size is in the range of 200-400 nm; and the particles obtained in Example 6 are sulfides, and the particle size is in the range of 10-30 nm. It can be reasonably expected that the obtained multi-element alloy has high catalytic activity and a wide range of applications. The specific test results are shown in Table 3. Figures 2 to 7

[0263] In summary, the light-absorbing material used in the preparation method provided by the present application has the ability to absorb light energy and release high temperature. The combination of laser treatment and light-absorbing material can overcome the problems in the prior art and significantly improve the performance of the obtained multi-element alloy and the preparation efficiency of the multi-element alloy. In addition, by adjusting the type, irradiation intensity and irradiation time of the laser in the laser treatment, as well as the type of the precursor, the ratio between the precursor and the light-absorbing material, the type, atomic ratio, particle size and crystal structure of the obtained multi-element alloy can be adjusted, thereby realizing the functionalization of the multi-element alloy, improving the activity and stability of the catalyst, and widening the application range of the obtained multi-element alloy. The preparation method provided by the present application also has the advantages of simple operation, easy industrialization and large-scale production and application, etc.

[0264] ​The embodiments of the present application are described in detail above with reference to the drawings, but the present application is not limited to the above-described embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present application.

Claims

1. A method for preparing a multi-element alloy for a catalyst, characterized in that, The preparation method includes: A mixture of light-absorbing material and precursor is processed using laser; the mass ratio of the precursor to the light-absorbing material is 1:0.12 to 2. The light-absorbing material includes at least one of carbon-based materials, molybdenum disulfide, tungsten disulfide, MXene, black phosphorus, and two-dimensional selenides; the carbon-based material is at least one of graphene oxide, graphene, graphynylene, carbon quantum dots, graphite, carbon nanotubes, fullerene, carbon paper, and carbon cloth. The precursor includes at least two of the following: cobalt-based materials, iron-based materials, nickel-based materials, copper-based materials, manganese-based materials, platinum-based materials, palladium-based materials, gold-based materials, indium-based materials, titanium-based materials, silver-based materials, ruthenium-based materials, iridium-based materials, chromium-based materials, tin-based materials, vanadium-based materials, lanthanum-based materials, cerium-based materials, antimony-based materials, tellurium-based materials, bismuth-based materials, niobium-based materials, tungsten-based materials, and molybdenum-based materials. The precursor is a compound of the target element, and the target element is the element that forms the multi-element alloy; The multi-element alloy includes a light-absorbing material and particles loaded on the surface of the light-absorbing material, wherein the particles are reaction products of the precursor.

2. The preparation method according to claim 1, characterized in that, The power of the laser ranges from 100 milliwatts to 2000 watts.

3. The preparation method according to claim 1, characterized in that, The precursor is composed of copper-based materials, manganese-based materials, bismuth-based materials, indium-based materials, and titanium-based materials.

4. The preparation method according to claim 1, characterized in that, The precursor is composed of molybdenum-based materials, chromium-based materials, ruthenium-based materials, iridium-based materials, tungsten-based materials, and tin-based materials.

5. The preparation method according to claim 1, characterized in that, The precursor is composed of copper-based materials, silver-based materials, cerium-based materials, molybdenum-based materials, niobium-based materials, tungsten-based materials, indium-based materials, and tellurium-based materials.

6. The preparation method according to claim 1, characterized in that, The precursor is composed of vanadium-based materials, manganese-based materials, cobalt-based materials, ruthenium-based materials, lanthanum-based materials, silver-based materials, gold-based materials, and antimony-based materials.

7. The preparation method according to any one of claims 1 to 6, characterized in that, The mixture also includes elemental additives, which include at least one of nitrogen source, phosphorus source and sulfur source.

8. The preparation method according to claim 7, characterized in that, The mass ratio of the elemental additive to the precursor is 1:0.3 to 0.

5.

9. A multi-element alloy prepared by the preparation method according to any one of claims 1 to 8.

10. The application of the multi-element alloy as described in claim 9 in the fields of batteries, total water splitting, and organic synthesis.

11. The application according to claim 10, characterized in that, The battery field includes at least one of zinc-air batteries, lithium-carbon dioxide batteries, and lithium-oxygen batteries.

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