WO2019227340A1 - Nano electrocatalyst of gold-nickel-sulfide core-shell structure and preparation method therefor - Google Patents

Nano electrocatalyst of gold-nickel-sulfide core-shell structure and preparation method therefor Download PDF

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WO2019227340A1
WO2019227340A1 PCT/CN2018/089028 CN2018089028W WO2019227340A1 WO 2019227340 A1 WO2019227340 A1 WO 2019227340A1 CN 2018089028 W CN2018089028 W CN 2018089028W WO 2019227340 A1 WO2019227340 A1 WO 2019227340A1
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gold
electrocatalyst
core
nickel
reaction
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PCT/CN2018/089028
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French (fr)
Chinese (zh)
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谷猛
蔡超
韩韶波
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南方科技大学
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Priority to PCT/CN2018/089028 priority Critical patent/WO2019227340A1/en
Priority to CN201880000462.XA priority patent/CN110799266B/en
Publication of WO2019227340A1 publication Critical patent/WO2019227340A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • B01J35/398—
    • B01J35/51—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • 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

Definitions

  • the invention belongs to the technical field of inorganic materials, and particularly relates to a nano-electrocatalyst with a gold-nickel sulfide core-shell structure and a preparation method thereof.
  • Electrocatalytic oxidation technology uses electricity as an energy source, and promotes the decomposition of water to produce hydrogen under the action of a catalyst (or promotes the half-reaction rate of water decomposition and oxygen precipitation to improve the efficiency of hydrogen production). Therefore, the preparation of efficient catalysts is extremely effective in utilizing the remaining electricity. important.
  • Transition metal chalcogenides are an important class of multifunctional materials. They have very broad application prospects in storage devices, catalysts, etc., and they have attracted the attention of researchers. However, pure-phase transition metal chalcogenides tend to be singular in nature. For example, when used as an electrocatalyst, the unit activity mass is relatively low, which cannot meet a wider demand. Therefore, it is particularly important to develop electrocatalysts with high active mass.
  • the embodiment of the invention provides a nano-electrocatalyst with a gold-nickel sulfide core-shell structure and a preparation method thereof, in order to solve the problem that the properties of pure-phase transition metal chalcogenides tend to be singular. Restricted issues.
  • an electrocatalyst is provided.
  • the electrocatalyst is a gold nickel sulfide core-shell structure nano-electrocatalyst.
  • the gold nickel sulfide core-shell structure nano-electrocatalyst includes a core and a package. A shell layer covering the surface of the core, wherein the core is a gold core, the shell is nickel sulfide, and the gold core is composed of nano-gold particles.
  • a method for preparing an electrocatalyst is provided.
  • the electrocatalyst is a gold-nickel sulfide core-shell structure nano-electrocatalyst.
  • the gold-nickel sulfide core-shell structure nano-electrocatalyst includes a core and a surface coated on the core.
  • a method for preparing the gold nickel sulfide core-shell structure nano-electrocatalyst includes the following steps:
  • a sulfur source is added and mixed to obtain a second mixed solution; the second mixed solution is subjected to a third heating under an inert atmosphere.
  • the reaction is subjected to extraction and purification treatment to obtain a gold nickel sulfide core-shell structure nano-electrocatalyst.
  • the electrocatalyst provided by the present invention uses nickel sulfide as a shell. Unlike traditional transition metal sulfides, nickel sulfide is a traditional band metal. Therefore, nickel sulfide has very low electrical resistance compared to most other sulfides, and it has a certain ability to catalyze water electrolysis. On this basis, a gold core composed of the nano-gold particles is used as a core.
  • the gold-nickel sulfide core-shell nanometer electrocatalyst of the present invention is different from bulk gold. The gold nanoparticles in the gold core form Au + during the electrocatalysis process, and cooperate with the nickel sulfide nanoparticles to accelerate the electron flow rate during the catalytic process.
  • the core-shell structure while maintaining the synergy between gold nanoparticles (Au) and nickel sulfide nanoparticles (Ni-S), can increase the effective catalytic area of Ni-S and provide Ni atom utilization.
  • the resulting gold-nickel sulfide core-shell structure nanoparticles can be used as an electrocatalyst, and when used as an electrocatalyst, it has a high unit active mass and has the advantages of wide adaptability.
  • a gold source is mixed with a ligand solution and reacted to prepare a precursor.
  • a nickel salt and a sulfur source are sequentially added to react to prepare a nanometer with gold core and nickel sulfide shell Electrocatalyst.
  • the method is simple in operation, mild in condition and easy to control, and the prepared gold-nickel sulfide core-shell structure nanoparticles have high unit active mass when used as an electrocatalyst.
  • Example 1 is an X-ray diffraction pattern of gold-nickel sulfide core-shell structure nanoparticles provided in Example 1 of the present invention
  • Example 2 is an electron microscope scanning transmission image of gold-nickel sulfide core-shell structure nanoparticles provided in Example 1 of the present invention
  • Example 3 is an electrochemical test chart of gold-nickel sulfide core-shell structure nanoparticles provided in Example 1 of the present invention.
  • first and second are only used for descriptive purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as “first” and “second” may explicitly or implicitly include one or more of the features. In the description of the present invention, the meaning of "plurality” is two or more, unless specifically defined otherwise.
  • One aspect of the embodiments of the present invention provides an electrocatalyst, wherein the electrocatalyst is a gold-nickel sulfide core-shell structure nano-electrocatalyst, and the gold-nickel sulfide core-shell structure nano-electrocatalyst includes a core and a core coating on a surface of the core.
  • the electrocatalyst provided by the embodiment of the present invention uses nickel sulfide with electrocatalytic activity as the shell (the substance that actually exerts the catalytic performance is set as the shell layer to participate in the reaction).
  • nickel sulfide is a traditional band metal. Therefore, nickel sulfide has very low electrical resistance compared to most other sulfides, and it has a certain ability to catalyze water electrolysis.
  • a gold core composed of the nano-gold particles is used as a core to promote the catalytic activity of nickel sulfide.
  • the gold-nickel sulfide core-shell nano-electrocatalyst is different from bulk gold.
  • the gold nanoparticles in the gold core form Au + in the electrocatalytic process, and cooperate with the nickel sulfide nanoparticles to accelerate the electron flow rate in the catalytic process.
  • the core-shell structure while maintaining the synergy between gold nanoparticles (Au) and nickel sulfide nanoparticles (Ni-S), can increase the effective catalytic area of Ni-S and provide Ni atom utilization.
  • the resulting gold-nickel sulfide core-shell structure nanoparticles can be used as an electrocatalyst, and when used as an electrocatalyst, it has a high unit active mass and has the advantages of wide adaptability.
  • the overall size of the gold-nickel sulfide nano-electrocatalyst with a core-shell structure that is, the particle size range is 18-32 nm.
  • the particle size of the nano-gold particles is 6-10 nm
  • the thickness of the shell layer is 0.2-8 nm (the particle size outside the shell layer is the particle size range of the gold core),
  • the thickness of the shell layer is more preferably 2-8 nm.
  • the electrocatalyst provided by the embodiment of the present invention can be prepared by the following method.
  • an embodiment of the present invention provides a method for preparing an electrocatalyst.
  • the electrocatalyst is a gold-nickel sulfide core-shell structure nano-electrocatalyst.
  • the gold-nickel sulfide core-shell structure nano-electrocatalyst includes a core and a coating on the core.
  • a method for preparing the gold nickel sulfide core-shell structure nano-electrocatalyst includes the following steps:
  • S01 Provide a gold source, dissolve the gold source in a ligand solution, and mix and process to form a precursor solution of gold and the ligand; under an inert atmosphere, subject the precursor solution to a first heating reaction;
  • a gold source is mixed with a ligand solution and reacted to prepare a precursor. After the precursor is heated and reacted, a nickel salt and a sulfur source are sequentially added to react to prepare gold as the core and nickel sulfide as the shell. Nano-electrocatalyst.
  • the method is simple in operation, mild in condition and easy to control, and the prepared gold-nickel sulfide core-shell structure nanoparticles have high unit active mass when used as an electrocatalyst.
  • a gold source for preparing the gold nickel sulfide core-shell structure nano-electrocatalyst is provided, and the gold source is a gold salt containing gold ions.
  • the gold salt is chloroauric acid, including chloroauric acid in water, and the specific structural formula can be characterized as HAuCl4 ⁇ xH2O.
  • a ligand solution is provided, and the gold source is mixed with the ligand solution to promote binding of the ligand to gold ions to form a precursor of gold and the ligand.
  • the ligand solution is an organic solvent containing a ligand, and in the present invention, the ligand is not only used as a solvent for dispersing a gold source, and subsequently added nickel salts and sulfur sources, but also as a reducing agent for Reduction of gold and nickel ions.
  • the ligand is oleylamine.
  • the oleylamine When used as a solvent, it is also used as a reducing agent and a surfactant during the first heating reaction and the second heating reaction in the embodiment of the present invention to reduce gold ions and nickel ions, and promote them to become nanoparticles, and Improve the dispersibility of nanoparticles. Further preferably, the mass percentage content of the oleylamine in the ligand solution is greater than 20%, so as to facilitate the effective exertion of the functions of its reducing agent and surfactant. Of course, it should be understood that oleylamine can be directly selected for the ligand solution.
  • the molar concentration of gold ions is 0.01-20 mmol / L. If the molar concentration of the gold ions is too high, a large range of gold particles will be formed, and the core-shell structure cannot be formed.
  • the molar concentration of gold ions is 1-15 mmol / L.
  • magnetic mixing is used for mixing treatment.
  • the precursor solution is subjected to a first heating reaction under an inert atmosphere.
  • gold ions in the solution are reduced by ligands (preferably oleylamine) to form product gold nanoparticles.
  • ligands preferably oleylamine
  • the ligand oleylamine is completely transformed from a reducing agent into a surfactant, which promotes The uniform dispersion of gold nanoparticles provides an excellent dispersion state for the subsequent formation of the core-shell structure.
  • the inert atmosphere referred to in the embodiments of the present invention refers to an oxygen-free system (a gas system containing no oxidant such as oxygen), and the gas and the reaction solution, the gas and the metal source (gold source, nickel source) in the oxygen-free system are prepared throughout.
  • the inert atmosphere is selected from one of an argon atmosphere, a nitrogen atmosphere, a hydrogen atmosphere, and a nitrogen dioxide atmosphere, and an argon atmosphere is preferably used.
  • an inert gas is passed into the reaction system at a gas flow rate of 0.01-50 ml / s, which is beneficial to forming a nanomaterial with uniform particles. If the flow velocity is too high, the size difference of the formed nanomaterials will be too large to form a uniform nanomaterial (that is, the nanoparticles grow too fast, causing some particles or even all of them to exceed the nanometer size range). More preferably, during the first heating reaction, an inert gas is passed into the reaction system at a gas flow rate of 10-40 ml / s.
  • the first heating reaction in which the gold ion is reduced by the ligand is performed at 120-200 ° C., and the reaction time is 0.01-5 hours. If the reaction temperature is too high, the reduction reaction cannot be performed efficiently or the reaction efficiency is low; if the reaction temperature is too high, it will lead to the secondary growth of the gold nanoparticles, and it will not be able to form a uniform nanomaterial (that is, the secondary growth of the nanoparticles will form a large size) Particles, causing some particles, or even all of them, to exceed the nanometer size range).
  • the temperature of the reaction system after the first heating reaction is lowered, so that the temperature of the reaction system is lower than 120 ° C. If the temperature after the cooling treatment is too high, after the nickel salt is added, nickel ions quickly participate in the reaction and quickly nucleate, so that it is impossible to obtain a uniform nanomaterial. Specifically, the temperature after cooling can be between 15-120 ° C. After cooling down, nickel salt was added.
  • the nickel salt is selected from, but not limited to, nickel chloride NiCl 2 , nickel sulfate NiSO 4 , nickel nitrate Ni (NO 3 ) 2 , nickel acetate Ni (Ac) 2 , nickel acetylacetonate Ni (acac) 2 and hydrates thereof.
  • At least one of the other nickel compounds can be selected as the nickel salt.
  • the added amount of the nickel salt satisfies: in the mixed solution after adding the nickel salt, the molar ratio of gold to nickel is 0.1-20: 1, so that the obtained gold-nickel sulfide core-shell structure nano-electrocatalyst is obtained.
  • the particle size of the gold core and the thickness of the shell layer are within the appropriate ranges. When used as an electrocatalyst, it has a high unit active mass.
  • the molar concentration of nickel ions is 0.01-400 mmol / L. If the concentration of the nickel ions is too high, the nucleation reaction is too fast, and uniformized nanoparticles cannot be obtained. More preferably, the molar concentration of nickel ions in the mixed solution after adding the nickel salt or the first mixed solution is 50-300 mmol / L.
  • mixing treatment is performed by stirring.
  • the stirring time is 0.1-5 hours, more preferably 1-3 hours; the temperature during stirring can be controlled at 15-180 ° C, and the stirring treatment is preferably performed at 60-100 ° C.
  • the first mixed solution is subjected to a temperature rise treatment to perform a second heating reaction.
  • the nickel ions in the solution are reduced and combined with the nano-gold particles in the solution to form gold-nickel nanoparticles.
  • the gold and nickel in the solution are all reduced to nanoparticles and the alloy Form exists.
  • the inert atmosphere referred to in the present invention, the selection of the inert gas, and the preferred method of addition can be performed with reference to step S01.
  • the second heating reaction is performed at 220-350 ° C, and the reaction time is 0.1-5 hours. If the reaction temperature is too low, nickel ions cannot be reduced; if the reaction temperature is too high, the solution is boiled, secondary agglomeration is liable to occur, and uniform nanomaterials cannot be obtained.
  • the reaction system after the first heating reaction is cooled down to a temperature lower than 120 ° C, a nickel salt is added, and the first In a mixed solution step, after adding the nickel salt, a boryl organic compound is added, and a first mixed solution is obtained after mixing.
  • the boryl organic compound can reduce the reaction rate as a reducing agent.
  • the boralkyl organic compound is selected from at least one of borane ammonia and tert-butyl alkylamine.
  • the molar ratio of the boryl organic compound to gold is 5: 1 to 40: 1, so that it can provide a good reduction effect, and will not The excessive growth of the boryl organic compound causes secondary growth.
  • the surfactant helps to improve the dispersibility and uniformity of the nanoparticles.
  • the surfactant is selected from at least one of oleic acid OA, trioctylphosphine oxide TOPO, and trioctylphosphine TOP.
  • the molar ratio of the surfactant to gold is 2: 1-100: 1, so as to ensure a better dispersion effect and prevent the agglomeration of the nanoparticles, and at the same time, It will not affect the occurrence of the reduction reaction because the content of the surfactant is too high, and eventually a uniform nanomaterial is obtained.
  • a nickel salt is added, and a first mixed solution is obtained after mixing.
  • a boryl organic compound and a surfactant are added and mixed to obtain a first mixed solution.
  • the molar ratio of the boryl organic compound to gold is 5: 1 to 40: 1, and the molar ratio of the surfactant to gold It is 2: 1-100: 1.
  • the temperature of the reaction system after the second heating reaction is lowered, so that the temperature of the reaction system is lower than 120 ° C. If the temperature after the cooling treatment is too high, after adding a sulfur source, it is easy to cause an explosion, and there is a hidden safety hazard. After cooling down, a sulfur source was added.
  • the sulfur source is a sulfur-containing compound that is miscible with a ligand solution, particularly an oleylamine solution, and is selected from, but not limited to, at least one of n-dodecanethiol, thiourea, and sulfur powder.
  • the added amount of the sulfur source satisfies: in the mixed solution after adding the sulfur source, the molar content of sulfur is 1.5-20 times the molar content of nickel, that is, the molar ratio of nickel to sulfur is 1: 1.5-20, This promotes the formation of nickel sulfide nanoparticles.
  • nickel acetylacetonate and n-dodecyl mercaptan are used as nickel salts and sulfur sources, respectively, to prepare nickel sulfide nanoparticles.
  • the gold nickel sulfide core-shell nano-electrocatalyst thus obtained has a uniform size and a very small size. Good dispersibility is conducive to improving catalytic properties.
  • other combinations of nickel salts and sulfur sources can also be used in the present invention.
  • the synthesized gold-nickel sulfide core-shell nanoparticles cannot ensure the dispersion well, and the catalytic properties are not as good as using nickel acetylacetonate and n-dodecanethiol respectively.
  • the gold-nickel sulfide core-shell nano-electrocatalyst prepared as a nickel salt and a sulfur source is good, but still has better catalytic activity than the existing electrocatalysts.
  • mixing treatment is performed by stirring.
  • the stirring time is 0.1-5 hours, more preferably 1-3 hours; the temperature during stirring can be controlled at 15-140 ° C, and the stirring treatment is preferably performed at 60-100 ° C.
  • the second mixed solution is heated up and subjected to a third heating reaction to promote the combination of the gold-nickel alloy and the sulfur source to generate a core-shell structure in which nickel sulfide nanoparticles are coated on the surface of the metal nanoparticles.
  • the inert atmosphere referred to in this step, the selection of the inert gas, and the preferred method of addition can be performed with reference to step S01.
  • the second heating reaction is performed at 220-250 ° C, and the reaction time is 0.1-2 hours. If the reaction temperature is too low, the reaction cannot be nucleated, and a core-shell structure cannot be obtained; if the reaction temperature is too high, a uniform nanomaterial cannot be obtained.
  • the reaction system is cooled to a temperature lower than 60 ° C, and an inert gas is continuously introduced to maintain an inert atmosphere.
  • the black product in the reaction system namely the gold nickel sulfide core-shell structure nano-electrocatalyst
  • the product is collected.
  • universal methods such as ultrasound, centrifugation, and filtration can be used for cleaning, and the gold-nickel sulfide core-shell structure nanoparticles are stored in a liquid or in a powder form.
  • the obtained gold-nickel sulfide core-shell structure nano-electrocatalyst has a core-shell structure, wherein the core is a gold core and the shell is nickel sulfide.
  • the overall size of the gold-nickel sulfide nano-electrocatalyst with a core-shell structure, that is, a particle size range is 18-32 nm.
  • a method for preparing an electrocatalyst wherein the electrocatalyst is a gold-nickel sulfide core-shell structure nano-electrocatalyst, and the gold-nickel sulfide core-shell structure nano-electrocatalyst includes a core and a shell layer covering a surface of the core, wherein, The inner core is a gold core, and the outer shell is nickel sulfide; a method for preparing the gold-nickel sulfide core-shell structure nano-electrocatalyst includes the following steps:
  • step S15 The product dispersion obtained in step S14 is dried in a blast drying box for 12 hours, and the product powder is the target product.
  • the gold-nickel sulfide core-shell structure nanoparticles prepared in Example 1 of the present invention have an overall material structure as shown in X-ray diffraction (Fig. 1); the overall size is 18 to 32 nanometers, and the core-shell configuration is in which gold is the core.
  • the shell layer is nickel sulfide, and there are voids between the core and the shell.
  • the specific configuration of the morphology is shown in the scanning transmission electron microscope ( Figure 2).
  • the gold-nickel sulfide core-shell structure nanoparticle agent catalyzed the alkaline electrolytic water decomposition experiment using conventional methods, specifically: taking a certain concentration of the electrocatalyst dispersion liquid (1-10 mg / mL), dropped on the surface of the glassy carbon electrode (3-6 mm diameter), dried naturally, and then a three-electrode system was selected and tested in a 1 mol / L KOH solution.

Abstract

A method for preparing an electrocatalyst, comprising the following steps: providing a gold source, dissolving said gold source in a ligand solution, and carrying out a mixing treatment to form a precursor solution of gold and the ligand; carrying out a first heating reaction on the precursor solution under an inert atmosphere; after a reaction system subjected to the first heating reaction is subject to a cooling treatment, adding a nickel salt, and mixing to obtain a first mixed solution; carrying out a second heating reaction on the first mixed solution under the inert atmosphere; after the reaction system subjected to the second heating reaction is subject to a cooling treatment, adding a sulfur source, and mixing to obtain a second mixed solution; carrying out a third heating reaction on the second mixed solution under the inert atmosphere, and performing an extraction and purification treatment to obtain a nano electrocatalyst of a gold-nickel-sulfide core-shell structure.

Description

金硫化镍核壳结构纳米电催化剂及其制备方法Gold nickel sulfide core-shell structure nano-electrocatalyst and preparation method thereof 技术领域Technical field
本发明属于无机材料技术领域，尤其涉及一种金硫化镍核壳结构纳米电催化剂及其制备方法。The invention belongs to the technical field of inorganic materials, and particularly relates to a nano-electrocatalyst with a gold-nickel sulfide core-shell structure and a preparation method thereof.
背景技术Background technique
电催化氧化技术以电作为能量来源，在催化剂作用下促进水分解制备氢气（或者促进水分解氧析出半反应速率，以提高制氢效率），所以，高效催化剂的制备在利用剩余电量方面是极为重要的。Electrocatalytic oxidation technology uses electricity as an energy source, and promotes the decomposition of water to produce hydrogen under the action of a catalyst (or promotes the half-reaction rate of water decomposition and oxygen precipitation to improve the efficiency of hydrogen production). Therefore, the preparation of efficient catalysts is extremely effective in utilizing the remaining electricity. important.
过渡族金属硫族化合物是一类重要的多功能材料，在储存器件、催化剂等方向中有着非常广阔的应用前景，因此受到广大科研人员的关注。然而，纯相的过渡族金属硫族化合物，其性质趋向于单一化，如用作电催化剂时单位活性质量较低，不能满足更加广阔的需求。因此，研发单位活性质量高的电催化剂显得尤为重要。Transition metal chalcogenides are an important class of multifunctional materials. They have very broad application prospects in storage devices, catalysts, etc., and they have attracted the attention of researchers. However, pure-phase transition metal chalcogenides tend to be singular in nature. For example, when used as an electrocatalyst, the unit activity mass is relatively low, which cannot meet a wider demand. Therefore, it is particularly important to develop electrocatalysts with high active mass.
技术问题technical problem
本发明实施例提供了一种金硫化镍核壳结构纳米电催化剂及其制备方法，以解决纯相过渡族金属硫族化合物性质趋向于单一化，作为电催化剂使用时单位活性质量较低，使用受限的问题。The embodiment of the invention provides a nano-electrocatalyst with a gold-nickel sulfide core-shell structure and a preparation method thereof, in order to solve the problem that the properties of pure-phase transition metal chalcogenides tend to be singular. Restricted issues.
技术解决方案Technical solutions
本发明实施例是这样实现的，第一方面，提供了一种电催化剂，所述电催化剂为金硫化镍核壳结构纳米电催化剂，所述金硫化镍核壳结构纳米电催化剂包括内核和包覆在所述内核表面的壳层，其中，所述内核为金核，所述外壳为硫化镍，且所述金核由纳米金颗粒组成。Embodiments of the present invention are implemented in this way. In a first aspect, an electrocatalyst is provided. The electrocatalyst is a gold nickel sulfide core-shell structure nano-electrocatalyst. The gold nickel sulfide core-shell structure nano-electrocatalyst includes a core and a package. A shell layer covering the surface of the core, wherein the core is a gold core, the shell is nickel sulfide, and the gold core is composed of nano-gold particles.
第二方面，提供了一种电催化剂的制备方法，所述电催化剂为金硫化镍核壳结构纳米电催化剂，所述金硫化镍核壳结构纳米电催化剂包括内核和包覆在所述内核表面的壳层，其中，所述内核为金核，所述外壳为硫化镍；所述金硫化镍核壳结构纳米电催化剂的制备方法，包括以下步骤：In a second aspect, a method for preparing an electrocatalyst is provided. The electrocatalyst is a gold-nickel sulfide core-shell structure nano-electrocatalyst. The gold-nickel sulfide core-shell structure nano-electrocatalyst includes a core and a surface coated on the core. A shell layer, wherein the core is a gold core and the shell is nickel sulfide; a method for preparing the gold nickel sulfide core-shell structure nano-electrocatalyst includes the following steps:
提供金源，将所述金源溶于配体溶液中，混合处理形成金与配体的前驱体溶液；在惰性气氛下，将所述前驱体溶液进行第一加热反应；Providing a gold source, dissolving the gold source in a ligand solution, and mixing and forming a precursor solution of gold and the ligand; under a inert atmosphere, subjecting the precursor solution to a first heating reaction;
将经所述第一加热反应后的反应体系降温处理至温度低于120℃后，加入镍盐，混合后得到第一混合溶液；在惰性气氛下，将所述第一混合溶液进行第二加热反应；After cooling the reaction system after the first heating reaction to a temperature lower than 120 ° C, adding a nickel salt and mixing to obtain a first mixed solution; under an inert atmosphere, heating the first mixed solution for a second time reaction;
将经所述第二加热反应后的反应体系降温处理至温度低于120℃后，加入硫源，混合后得到第二混合溶液；在惰性气氛下，将所述第二混合溶液进行第三加热反应，经提取纯化处理，得到金硫化镍核壳结构纳米电催化剂。After cooling the reaction system after the second heating reaction to a temperature lower than 120 ° C, a sulfur source is added and mixed to obtain a second mixed solution; the second mixed solution is subjected to a third heating under an inert atmosphere. The reaction is subjected to extraction and purification treatment to obtain a gold nickel sulfide core-shell structure nano-electrocatalyst.
有益效果Beneficial effect
本发明提供的电催化剂，以硫化镍作为外壳。不同于传统过渡族金属硫化物，硫化镍是一种传统带金属，因此，硫化镍相对于其他大部分硫化物而言电阻非常小，且其有一定的水电解催化能力。在此基础上，以所述纳米金颗粒组成的金核作为内核。本发明金硫化镍核壳结构纳米电催化剂，不同于体相金，金核中的纳米金颗粒在电催化过程中形成Au+，与硫化镍纳米颗粒协同，加速催化过程中电子流速。而核壳结构，在保持纳米金颗粒（Au）与硫化镍纳米颗粒（Ni-S）协同作用的同时，能够提高Ni-S有效催化面积，提供Ni原子利用率。由此形成的金硫化镍核壳结构纳米颗粒，可以作为电催化剂，且作为电催化剂使用时，具有很高的单位活性质量，且具有适应性广的优点。The electrocatalyst provided by the present invention uses nickel sulfide as a shell. Unlike traditional transition metal sulfides, nickel sulfide is a traditional band metal. Therefore, nickel sulfide has very low electrical resistance compared to most other sulfides, and it has a certain ability to catalyze water electrolysis. On this basis, a gold core composed of the nano-gold particles is used as a core. The gold-nickel sulfide core-shell nanometer electrocatalyst of the present invention is different from bulk gold. The gold nanoparticles in the gold core form Au + during the electrocatalysis process, and cooperate with the nickel sulfide nanoparticles to accelerate the electron flow rate during the catalytic process. The core-shell structure, while maintaining the synergy between gold nanoparticles (Au) and nickel sulfide nanoparticles (Ni-S), can increase the effective catalytic area of Ni-S and provide Ni atom utilization. The resulting gold-nickel sulfide core-shell structure nanoparticles can be used as an electrocatalyst, and when used as an electrocatalyst, it has a high unit active mass and has the advantages of wide adaptability.
本发明提供的电催化剂的制备方法，金源与配体溶液混合后反应制备前驱体，将前驱体加热反应后，依次加入镍盐、硫源反应，制备内核为金、外壳为硫化镍的纳米电催化剂。该方法操作简单，条件温和易控，且制备得到的金硫化镍核壳结构纳米颗粒，用作电催化剂使用时，具有很高的单位活性质量。According to the method for preparing an electrocatalyst provided by the present invention, a gold source is mixed with a ligand solution and reacted to prepare a precursor. After the precursor is heated and reacted, a nickel salt and a sulfur source are sequentially added to react to prepare a nanometer with gold core and nickel sulfide shell Electrocatalyst. The method is simple in operation, mild in condition and easy to control, and the prepared gold-nickel sulfide core-shell structure nanoparticles have high unit active mass when used as an electrocatalyst.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1是本发明实施例1提供的金硫化镍核壳结构纳米颗粒的X射线衍射图；1 is an X-ray diffraction pattern of gold-nickel sulfide core-shell structure nanoparticles provided in Example 1 of the present invention;
图2是本发明实施例1提供的金硫化镍核壳结构纳米颗粒的电子显微镜扫描透射图；2 is an electron microscope scanning transmission image of gold-nickel sulfide core-shell structure nanoparticles provided in Example 1 of the present invention;
图3是本发明实施例1提供的金硫化镍核壳结构纳米颗粒的电化学测试图。3 is an electrochemical test chart of gold-nickel sulfide core-shell structure nanoparticles provided in Example 1 of the present invention.
本发明的实施方式Embodiments of the invention
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the objectives, technical solutions, and advantages of the present invention clearer, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.
在本发明的描述中，需要理解的是，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本发明的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。In the description of the present invention, it should be understood that the terms “first” and “second” are only used for descriptive purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features. In the description of the present invention, the meaning of "plurality" is two or more, unless specifically defined otherwise.
本发明实施例一方面提供了一种电催化剂，所述电催化剂为金硫化镍核壳结构纳米电催化剂，所述金硫化镍核壳结构纳米电催化剂包括内核和包覆在所述内核表面的壳层，其中，所述内核为金核，所述外壳为硫化镍，且所述金核由纳米金颗粒组成。One aspect of the embodiments of the present invention provides an electrocatalyst, wherein the electrocatalyst is a gold-nickel sulfide core-shell structure nano-electrocatalyst, and the gold-nickel sulfide core-shell structure nano-electrocatalyst includes a core and a core coating on a surface of the core. A shell layer, wherein the inner core is a gold core, the outer shell is nickel sulfide, and the gold core is composed of nano-gold particles.
本发明实施例提供的电催化剂，以具有电催化活性的硫化镍作为外壳（实际发挥催化性能的物质设置为壳层参与反应）。不同于传统过渡族金属硫化物，硫化镍是一种传统带金属，因此，硫化镍相对于其他大部分硫化物而言电阻非常小，且其有一定的水电解催化能力。在此基础上，以所述纳米金颗粒组成的金核作为内核，来促进硫化镍的催化活性。本发明实施例金硫化镍核壳结构纳米电催化剂，不同于体相金，金核中的纳米金颗粒在电催化过程中形成Au+，与硫化镍纳米颗粒协同，加速催化过程中电子流速。而核壳结构，在保持纳米金颗粒（Au）与硫化镍纳米颗粒（Ni-S）协同作用的同时，能够提高Ni-S有效催化面积，提供Ni原子利用率。由此形成的金硫化镍核壳结构纳米颗粒，可以作为电催化剂，且作为电催化剂使用时，具有很高的单位活性质量，且具有适应性广的优点。The electrocatalyst provided by the embodiment of the present invention uses nickel sulfide with electrocatalytic activity as the shell (the substance that actually exerts the catalytic performance is set as the shell layer to participate in the reaction). Unlike traditional transition metal sulfides, nickel sulfide is a traditional band metal. Therefore, nickel sulfide has very low electrical resistance compared to most other sulfides, and it has a certain ability to catalyze water electrolysis. On this basis, a gold core composed of the nano-gold particles is used as a core to promote the catalytic activity of nickel sulfide. In the embodiment of the present invention, the gold-nickel sulfide core-shell nano-electrocatalyst is different from bulk gold. The gold nanoparticles in the gold core form Au + in the electrocatalytic process, and cooperate with the nickel sulfide nanoparticles to accelerate the electron flow rate in the catalytic process. The core-shell structure, while maintaining the synergy between gold nanoparticles (Au) and nickel sulfide nanoparticles (Ni-S), can increase the effective catalytic area of Ni-S and provide Ni atom utilization. The resulting gold-nickel sulfide core-shell structure nanoparticles can be used as an electrocatalyst, and when used as an electrocatalyst, it has a high unit active mass and has the advantages of wide adaptability.
具体的，所述金硫化镍核壳结构纳米电催化剂的整体尺寸即粒径范围为18-32nm。进一步的，本发明实施例中，所述纳米金颗粒的粒径尺寸为6-10nm，所述壳层的厚度为0.2-8nm（壳层以外的粒径大小为金核的粒径范围），所述壳层的厚度更优选为2-8nm。本发明实施例中，由于Au在金硫化镍核壳结构纳米电催化剂中发挥协同作用，其本身并不直接地参与催化反应，因此，Au：Ni摩尔比例越小，单位水分解需要用到的镍原子越少（比如1 ummol水分解），即Ni原子利用率越高。于电催化剂本身而言，过薄的外壳厚度，会导致催化剂过早失活（电催化过程中电氧化刻蚀Ni原子），所以，形成一定厚度的硫化镍外壳对保持电催化剂的催化效率和稳定性非常重要。Specifically, the overall size of the gold-nickel sulfide nano-electrocatalyst with a core-shell structure, that is, the particle size range is 18-32 nm. Further, in the embodiment of the present invention, the particle size of the nano-gold particles is 6-10 nm, and the thickness of the shell layer is 0.2-8 nm (the particle size outside the shell layer is the particle size range of the gold core), The thickness of the shell layer is more preferably 2-8 nm. In the embodiment of the present invention, since Au plays a synergistic role in the gold-nickel sulfide core-shell nano-electrocatalyst, and itself does not directly participate in the catalytic reaction, therefore, the smaller the molar ratio of Au: Ni, the more unit water decomposition needs Fewer nickel atoms (such as 1 ummol water decomposition), the higher the Ni atom utilization rate. For the electrocatalyst itself, too thin shell thickness will cause the catalyst to deactivate prematurely (electro-oxidation etches Ni atoms during the electrocatalytic process). Therefore, the formation of a nickel sulfide shell with a certain thickness can maintain the catalytic efficiency and Stability is very important.
本发明实施例提供的所述电催化剂，可以通过下述方法制备获得。The electrocatalyst provided by the embodiment of the present invention can be prepared by the following method.
相应的，本发明实施例提供了一种电催化剂的制备方法，所述电催化剂为金硫化镍核壳结构纳米电催化剂，所述金硫化镍核壳结构纳米电催化剂包括内核和包覆在所述内核表面的壳层，其中，所述内核为金核，所述外壳为硫化镍；所述金硫化镍核壳结构纳米电催化剂的制备方法，包括以下步骤：Accordingly, an embodiment of the present invention provides a method for preparing an electrocatalyst. The electrocatalyst is a gold-nickel sulfide core-shell structure nano-electrocatalyst. The gold-nickel sulfide core-shell structure nano-electrocatalyst includes a core and a coating on the core. The shell layer on the surface of the inner core, wherein the inner core is a gold core and the outer shell is nickel sulfide; a method for preparing the gold nickel sulfide core-shell structure nano-electrocatalyst includes the following steps:
S01.提供金源，将所述金源溶于配体溶液中，混合处理形成金与配体的前驱体溶液；在惰性气氛下，将所述前驱体溶液进行第一加热反应；S01. Provide a gold source, dissolve the gold source in a ligand solution, and mix and process to form a precursor solution of gold and the ligand; under an inert atmosphere, subject the precursor solution to a first heating reaction;
S02.将经所述第一加热反应后的反应体系降温处理至温度低于120℃后，加入镍盐，混合后得到第一混合溶液；在惰性气氛下，将所述第一混合溶液进行第二加热反应；S02. After cooling the reaction system after the first heating reaction to a temperature lower than 120 ° C, adding a nickel salt and mixing to obtain a first mixed solution; in an inert atmosphere, subjecting the first mixed solution to a first Two heating reaction;
S03.将经所述第二加热反应后的反应体系降温处理至温度低于120℃后，加入硫源，混合后得到第二混合溶液；在惰性气氛下，将所述第二混合溶液进行第三加热反应，经提取纯化处理，得到金硫化镍核壳结构纳米电催化剂。S03. After cooling the reaction system after the second heating reaction to a temperature lower than 120 ° C, adding a sulfur source and mixing to obtain a second mixed solution; under an inert atmosphere, subjecting the second mixed solution to the first Three heating reactions, and extraction and purification treatment, to obtain a gold nickel sulfide core-shell structure nano-electrocatalyst.
本发明实施例提供的电催化剂的制备方法，金源与配体溶液混合后反应制备前驱体，将前驱体加热反应后，依次加入镍盐、硫源反应，制备内核为金、外壳为硫化镍的纳米电催化剂。该方法操作简单，条件温和易控，且制备得到的金硫化镍核壳结构纳米颗粒，用作电催化剂使用时，具有很高的单位活性质量。In the method for preparing an electrocatalyst provided in the embodiment of the present invention, a gold source is mixed with a ligand solution and reacted to prepare a precursor. After the precursor is heated and reacted, a nickel salt and a sulfur source are sequentially added to react to prepare gold as the core and nickel sulfide as the shell. Nano-electrocatalyst. The method is simple in operation, mild in condition and easy to control, and the prepared gold-nickel sulfide core-shell structure nanoparticles have high unit active mass when used as an electrocatalyst.
具体的，上述步骤S01中，提供制备所述金硫化镍核壳结构纳米电催化剂的金源，所述金源为含金离子的金盐。优选的，所述金盐为氯金酸，包括水喝氯金酸，具体结构式可表征为HAuCl4·xH2O。Specifically, in the above step S01, a gold source for preparing the gold nickel sulfide core-shell structure nano-electrocatalyst is provided, and the gold source is a gold salt containing gold ions. Preferably, the gold salt is chloroauric acid, including chloroauric acid in water, and the specific structural formula can be characterized as HAuCl4 · xH2O.
提供配体溶液，将所述金源与所述配体溶液进行混合处理，促使配体与金离子结合，形成金与配体的前驱体。其中，所述配体溶液为含有配体的有机溶剂，所述配体在本发明中，不仅作为分散金源、以及后续添加的镍盐、硫源的溶剂，同时，作为还原剂，用于还原金离子和镍离子。优选的，所述配体为油胺。所述油胺作为溶剂的同时，还作为本发明实施例第一加热反应、第二加热反应过程中的还原剂和表面活性剂，用于还原金离子与镍离子，促使其成为纳米粒子，并提高纳米粒子的分散性。进一步优选的，所述油胺在所述配体溶液中的质量百分含量大于20%，从而有利于其还原剂和表面活性剂作用的有效发挥。当然，应当理解，所述配体溶液可以直接选择油胺。A ligand solution is provided, and the gold source is mixed with the ligand solution to promote binding of the ligand to gold ions to form a precursor of gold and the ligand. Wherein, the ligand solution is an organic solvent containing a ligand, and in the present invention, the ligand is not only used as a solvent for dispersing a gold source, and subsequently added nickel salts and sulfur sources, but also as a reducing agent for Reduction of gold and nickel ions. Preferably, the ligand is oleylamine. When the oleylamine is used as a solvent, it is also used as a reducing agent and a surfactant during the first heating reaction and the second heating reaction in the embodiment of the present invention to reduce gold ions and nickel ions, and promote them to become nanoparticles, and Improve the dispersibility of nanoparticles. Further preferably, the mass percentage content of the oleylamine in the ligand solution is greater than 20%, so as to facilitate the effective exertion of the functions of its reducing agent and surfactant. Of course, it should be understood that oleylamine can be directly selected for the ligand solution.
金源与配体溶液形成的混合溶液或所述前驱体溶液中，金离子的摩尔浓度为0.01-20mmol/L。若所述金离子的摩尔浓度过高，将导致形成大范围的金颗粒，从而无法形成核壳该结构。优选的，金源与配体溶液形成的混合溶液，金离子的摩尔浓度为1-15mmol/L。In the mixed solution formed by the gold source and the ligand solution or the precursor solution, the molar concentration of gold ions is 0.01-20 mmol / L. If the molar concentration of the gold ions is too high, a large range of gold particles will be formed, and the core-shell structure cannot be formed. Preferably, in a mixed solution formed by the gold source and the ligand solution, the molar concentration of gold ions is 1-15 mmol / L.
本发明实施例中，优选的，为了更好地促使配体与金离子充分结合，形成稳定的金与配体的前驱体，采用磁力搅拌进行混合处理。In the embodiment of the present invention, in order to better promote the sufficient binding of the ligand to the gold ion to form a stable precursor of gold and the ligand, magnetic mixing is used for mixing treatment.
在惰性气氛下，将所述前驱体溶液进行第一加热反应。所述第一加热反应过程中，溶液中的金离子被配体（优选为油胺）还原形成产物纳米金颗粒，同时，所述配体油胺由还原剂角色彻底转变为表面活性剂，促进纳米金颗粒的均匀分散，为后续形成核壳结构提供优异的分散状态。本发明实施例所指的惰性气氛，是指无氧体系（不含氧气等氧化剂的气体体系），无氧体系中的气体与反应溶液、气体与金属源（金源、镍源）在整个制备方法过程中，不会发生物理化学反应。具体的，所述惰性气氛选自氩气气氛、氮气气氛、氢气气氛、二氧化氮气氛中的一种，优选采用氩气气氛。进一步优选的，第一加热反应过程中，以0.01-50ml/s的气流速度在反应体系中通入惰性气体，有利于形成颗粒均一化的纳米材料。若流速过高情况下，会导致形成的纳米材料尺寸差异过大，无法形成均一化的纳米材料（即纳米颗粒过快生长，导致部分颗粒、甚至全部颗粒尺寸超出纳米尺寸范围）。更优选的，第一加热反应过程中，以10-40ml/s的气流速度在反应体系中通入惰性气体。The precursor solution is subjected to a first heating reaction under an inert atmosphere. During the first heating reaction, gold ions in the solution are reduced by ligands (preferably oleylamine) to form product gold nanoparticles. At the same time, the ligand oleylamine is completely transformed from a reducing agent into a surfactant, which promotes The uniform dispersion of gold nanoparticles provides an excellent dispersion state for the subsequent formation of the core-shell structure. The inert atmosphere referred to in the embodiments of the present invention refers to an oxygen-free system (a gas system containing no oxidant such as oxygen), and the gas and the reaction solution, the gas and the metal source (gold source, nickel source) in the oxygen-free system are prepared throughout. During the method, no physical and chemical reactions occur. Specifically, the inert atmosphere is selected from one of an argon atmosphere, a nitrogen atmosphere, a hydrogen atmosphere, and a nitrogen dioxide atmosphere, and an argon atmosphere is preferably used. Further preferably, in the first heating reaction process, an inert gas is passed into the reaction system at a gas flow rate of 0.01-50 ml / s, which is beneficial to forming a nanomaterial with uniform particles. If the flow velocity is too high, the size difference of the formed nanomaterials will be too large to form a uniform nanomaterial (that is, the nanoparticles grow too fast, causing some particles or even all of them to exceed the nanometer size range). More preferably, during the first heating reaction, an inert gas is passed into the reaction system at a gas flow rate of 10-40 ml / s.
优选的，所述金离子被所述配体还原的所述第一加热反应在120-200℃条件下进行，反应时间为0.01-5小时。若反应温度过高，则还原反应无法有效进行，或者反应效率偏低；若反应温度过高会导致纳米金颗粒的二次生长，无法形成均一化纳米材料（即纳米颗粒二次生长形成大尺寸颗粒，导致部分颗粒、甚至全部颗粒尺寸超出纳米尺寸范围）。Preferably, the first heating reaction in which the gold ion is reduced by the ligand is performed at 120-200 ° C., and the reaction time is 0.01-5 hours. If the reaction temperature is too high, the reduction reaction cannot be performed efficiently or the reaction efficiency is low; if the reaction temperature is too high, it will lead to the secondary growth of the gold nanoparticles, and it will not be able to form a uniform nanomaterial (that is, the secondary growth of the nanoparticles will form a large size) Particles, causing some particles, or even all of them, to exceed the nanometer size range).
上述步骤S02中，将经所述第一加热反应后的反应体系降温处理，使反应体系的温度低于120℃。若降温处理后的温度过高，则添加镍盐后，镍离子迅速参与反应，快速成核，从而无法获取均一化纳米材料。具体的，降温后的温度可在15-120℃之间。降温后，加入镍盐。所述镍盐选自但不限于氯化镍NiCl 2、硫酸镍NiSO 4、硝酸镍Ni(NO 3) 2、醋酸镍Ni(Ac) 2、乙酰丙酮镍Ni(acac) 2及其水合物中的至少一种，也可选择其他镍化合物作为镍盐。优选的，所述镍盐的添加量满足：加入所述镍盐后的混合溶液中，金与镍的摩尔比为0.1-20：1，从而使得得到的金硫化镍核壳结构纳米电催化剂中，金核的粒径、外壳层的厚度在合适的范围内，用作电催化剂时，具有高单位活性质量。 In the above step S02, the temperature of the reaction system after the first heating reaction is lowered, so that the temperature of the reaction system is lower than 120 ° C. If the temperature after the cooling treatment is too high, after the nickel salt is added, nickel ions quickly participate in the reaction and quickly nucleate, so that it is impossible to obtain a uniform nanomaterial. Specifically, the temperature after cooling can be between 15-120 ° C. After cooling down, nickel salt was added. The nickel salt is selected from, but not limited to, nickel chloride NiCl 2 , nickel sulfate NiSO 4 , nickel nitrate Ni (NO 3 ) 2 , nickel acetate Ni (Ac) 2 , nickel acetylacetonate Ni (acac) 2 and hydrates thereof. At least one of the other nickel compounds can be selected as the nickel salt. Preferably, the added amount of the nickel salt satisfies: in the mixed solution after adding the nickel salt, the molar ratio of gold to nickel is 0.1-20: 1, so that the obtained gold-nickel sulfide core-shell structure nano-electrocatalyst is obtained. The particle size of the gold core and the thickness of the shell layer are within the appropriate ranges. When used as an electrocatalyst, it has a high unit active mass.
进一步的，加入所述镍盐后的混合溶液或所述第一混合溶液中，镍离子的摩尔浓度为0.01-400mmol/L。若所述镍离子的浓度过高，成核反应过快，无法获得均一化纳米颗粒。更优选的，加入所述镍盐后的混合溶液或所述第一混合溶液中，镍离子的摩尔浓度为50-300mmol/L。Further, in the mixed solution or the first mixed solution after adding the nickel salt, the molar concentration of nickel ions is 0.01-400 mmol / L. If the concentration of the nickel ions is too high, the nucleation reaction is too fast, and uniformized nanoparticles cannot be obtained. More preferably, the molar concentration of nickel ions in the mixed solution after adding the nickel salt or the first mixed solution is 50-300 mmol / L.
本发明实施例中，优选的，为了更好地促使纳米金颗粒与镍离子均匀分散、充分结合，进而获得均一化材料，采用搅拌进行混合处理。搅拌时间为0.1-5小时，更优选为1-3小时；搅拌时的温度可控制在15-180℃，优选在60-100℃条件下进行搅拌处理。In the embodiment of the present invention, preferably, in order to better promote the uniform dispersion and sufficient combination of the nano-gold particles and nickel ions to obtain a homogenized material, mixing treatment is performed by stirring. The stirring time is 0.1-5 hours, more preferably 1-3 hours; the temperature during stirring can be controlled at 15-180 ° C, and the stirring treatment is preferably performed at 60-100 ° C.
在惰性气氛下，将所述第一混合溶液升温处理，进行第二加热反应。所述第二加热反应过程中，溶液中的镍离子被还原，与溶液中的纳米金颗粒结合生成金镍纳米粒子，此时，溶液中的金、镍均由被还原为纳米粒子，以合金形式存在。本发明所指的惰性气氛，及其惰性气体的选择、优选添加方式，均可参照步骤S01进行。优选的，所述第二加热反应在220-350℃条件下进行，反应时间为0.1-5小时。若反应温度过低，则镍离子无法还原；若反应温度过高，则溶液沸腾，容易发生二次团聚，无法获取均一化纳米材料。Under an inert atmosphere, the first mixed solution is subjected to a temperature rise treatment to perform a second heating reaction. During the second heating reaction, the nickel ions in the solution are reduced and combined with the nano-gold particles in the solution to form gold-nickel nanoparticles. At this time, the gold and nickel in the solution are all reduced to nanoparticles and the alloy Form exists. The inert atmosphere referred to in the present invention, the selection of the inert gas, and the preferred method of addition can be performed with reference to step S01. Preferably, the second heating reaction is performed at 220-350 ° C, and the reaction time is 0.1-5 hours. If the reaction temperature is too low, nickel ions cannot be reduced; if the reaction temperature is too high, the solution is boiled, secondary agglomeration is liable to occur, and uniform nanomaterials cannot be obtained.
上述步骤S02中，在上述实施例的基础上，作为一种优选实施方式，将经所述第一加热反应后的反应体系降温处理至温度低于120℃后，加入镍盐，混合后得到第一混合溶液的步骤中，在加入所述镍盐后，加入硼烷基有机化合物，混合后得到第一混合溶液。所述硼烷基有机化合物作为还原剂，可以提升反应速率。优选的，所述硼烷基有机化合物时，所述硼烷基有机化合物选自硼烷氨、叔丁基烷胺中的至少一种。进一步优选的，引入硼烷基有机化合物后的混合溶液中，所述硼烷基有机化合物与金的摩尔比为5:1-40:1，从而可以提供较好的还原效果，且也不会因为所述硼烷基有机化合物的添加量过高造成二次生长。In the above step S02, based on the above examples, as a preferred embodiment, the reaction system after the first heating reaction is cooled down to a temperature lower than 120 ° C, a nickel salt is added, and the first In a mixed solution step, after adding the nickel salt, a boryl organic compound is added, and a first mixed solution is obtained after mixing. The boryl organic compound can reduce the reaction rate as a reducing agent. Preferably, in the case of the boralkyl organic compound, the boralkyl organic compound is selected from at least one of borane ammonia and tert-butyl alkylamine. Further preferably, in the mixed solution after the introduction of the boryl organic compound, the molar ratio of the boryl organic compound to gold is 5: 1 to 40: 1, so that it can provide a good reduction effect, and will not The excessive growth of the boryl organic compound causes secondary growth.
作为另一种优选实施方式，将经所述第一加热反应后的反应体系降温处理至温度低于120℃后，加入镍盐，混合后得到第一混合溶液的步骤中，在加入所述镍盐后，加入表面活性剂，混合后得到第一混合溶液。所述表面活性剂有助于提高纳米粒子的分散性和均匀性。优选的，所述表面活性剂选自油酸OA、三辛基氧化膦TOPO、三辛基膦TOP中的至少一种。进一步优选的，引入表面活性剂后的混合溶液中，所述表面活性剂与金的摩尔比为2:1-100:1，从而可以在保证较好的分散效果，防止纳米粒子团聚，同时，也不会因为所述表面活性剂含量过高而影响还原反应的发生，最终得到均一化纳米材料。As another preferred embodiment, after cooling the reaction system after the first heating reaction to a temperature lower than 120 ° C., adding a nickel salt, and obtaining a first mixed solution after mixing, adding the nickel After the salt, a surfactant is added and mixed to obtain a first mixed solution. The surfactant helps to improve the dispersibility and uniformity of the nanoparticles. Preferably, the surfactant is selected from at least one of oleic acid OA, trioctylphosphine oxide TOPO, and trioctylphosphine TOP. Further preferably, in the mixed solution after introducing the surfactant, the molar ratio of the surfactant to gold is 2: 1-100: 1, so as to ensure a better dispersion effect and prevent the agglomeration of the nanoparticles, and at the same time, It will not affect the occurrence of the reduction reaction because the content of the surfactant is too high, and eventually a uniform nanomaterial is obtained.
作为再一种优选实施方式，将经所述第一加热反应后的反应体系降温处理至温度低于120℃后，加入镍盐，混合后得到第一混合溶液的步骤中，在加入所述镍盐后，加入硼烷基有机化合物和表面活性剂，混合后得到第一混合溶液。优选的，引入硼烷基有机化合物和表面活性剂后的混合溶液中，所述硼烷基有机化合物与金的摩尔比为5:1-40:1，所述表面活性剂与金的摩尔比为2:1-100:1。As another preferred embodiment, after the temperature of the reaction system after the first heating reaction is lowered to less than 120 ° C., a nickel salt is added, and a first mixed solution is obtained after mixing. In the step of adding the nickel, After the salt, a boryl organic compound and a surfactant are added and mixed to obtain a first mixed solution. Preferably, in the mixed solution after introducing the boryl organic compound and a surfactant, the molar ratio of the boryl organic compound to gold is 5: 1 to 40: 1, and the molar ratio of the surfactant to gold It is 2: 1-100: 1.
上述步骤S03中，将经所述第二加热反应后的反应体系降温处理，使反应体系的温度低于120℃。若降温处理后的温度过高，则添加硫源后，容易引发***，存在安全隐患。降温后，加入硫源。所述硫源为能与配体溶液特别是油胺溶液互溶的含硫化合物，选自但不限于正十二硫醇、硫脲、硫粉中的至少一种。优选的，所述硫源的添加量满足：加入所述硫源后的混合溶液中，硫摩尔含量为摩尔含量镍的1.5~20倍，即镍与硫的摩尔比为1:1.5-20，从而促使硫化镍纳米颗粒的形成。In the above step S03, the temperature of the reaction system after the second heating reaction is lowered, so that the temperature of the reaction system is lower than 120 ° C. If the temperature after the cooling treatment is too high, after adding a sulfur source, it is easy to cause an explosion, and there is a hidden safety hazard. After cooling down, a sulfur source was added. The sulfur source is a sulfur-containing compound that is miscible with a ligand solution, particularly an oleylamine solution, and is selected from, but not limited to, at least one of n-dodecanethiol, thiourea, and sulfur powder. Preferably, the added amount of the sulfur source satisfies: in the mixed solution after adding the sulfur source, the molar content of sulfur is 1.5-20 times the molar content of nickel, that is, the molar ratio of nickel to sulfur is 1: 1.5-20, This promotes the formation of nickel sulfide nanoparticles.
作为具体优选实施例，采用乙酰丙酮镍与正十二硫醇分别作为镍盐和硫源，反应制备硫化镍纳米粒子，由此得到的金硫化镍核壳结构纳米电催化剂具有均一的尺度和很好的分散性，有利于提高催化性质。当然，其他镍盐和硫源的组合也可以用于本发明中，合成的金硫化镍核壳结构纳米颗粒不能很好的保证分散性，催化性质不如采用乙酰丙酮镍与正十二硫醇分别作为镍盐和硫源制备的金硫化镍核壳结构纳米电催化剂好，但仍然较现有的电催化剂具有很好的催化活性。As a specific preferred embodiment, nickel acetylacetonate and n-dodecyl mercaptan are used as nickel salts and sulfur sources, respectively, to prepare nickel sulfide nanoparticles. The gold nickel sulfide core-shell nano-electrocatalyst thus obtained has a uniform size and a very small size. Good dispersibility is conducive to improving catalytic properties. Of course, other combinations of nickel salts and sulfur sources can also be used in the present invention. The synthesized gold-nickel sulfide core-shell nanoparticles cannot ensure the dispersion well, and the catalytic properties are not as good as using nickel acetylacetonate and n-dodecanethiol respectively. The gold-nickel sulfide core-shell nano-electrocatalyst prepared as a nickel salt and a sulfur source is good, but still has better catalytic activity than the existing electrocatalysts.
本发明实施例中，优选的，为了更好地金镍合金与硫源充分结合，采用搅拌进行混合处理。搅拌时间为0.1-5小时，更优选为1-3小时；搅拌时的温度可控制在15-140℃，优选在60-100℃条件下进行搅拌处理。In the embodiment of the present invention, it is preferable that, in order to better fully combine the gold-nickel alloy with the sulfur source, mixing treatment is performed by stirring. The stirring time is 0.1-5 hours, more preferably 1-3 hours; the temperature during stirring can be controlled at 15-140 ° C, and the stirring treatment is preferably performed at 60-100 ° C.
在惰性气氛下，将所述第二混合溶液升温处理，进行第三加热反应，促使金镍合金与硫源结合，生成硫化镍纳米颗粒包覆在金属纳米颗粒表面的核壳结构。该步骤所指的惰性气氛，及其惰性气体的选择、优选添加方式，均可参照步骤S01进行。优选的，所述第二加热反应在220-250℃条件下进行，反应时间为0.1-2小时。若反应温度过低，则无法反应成核，得不到核壳结构；若反应温度过高，则无法获取均一化纳米材料。Under an inert atmosphere, the second mixed solution is heated up and subjected to a third heating reaction to promote the combination of the gold-nickel alloy and the sulfur source to generate a core-shell structure in which nickel sulfide nanoparticles are coated on the surface of the metal nanoparticles. The inert atmosphere referred to in this step, the selection of the inert gas, and the preferred method of addition can be performed with reference to step S01. Preferably, the second heating reaction is performed at 220-250 ° C, and the reaction time is 0.1-2 hours. If the reaction temperature is too low, the reaction cannot be nucleated, and a core-shell structure cannot be obtained; if the reaction temperature is too high, a uniform nanomaterial cannot be obtained.
反应结束后，将反应体系降温处理，使温度低于60℃，持续通入惰性气体，保持惰性气氛。After the reaction is completed, the reaction system is cooled to a temperature lower than 60 ° C, and an inert gas is continuously introduced to maintain an inert atmosphere.
进一步的，将反应体系中的黑色产物即金硫化镍核壳结构纳米电催化剂进行提取纯化，收集产物。具体的，可以经过超声、离心、过滤等普适性方法实现清洗，将金硫化镍核壳结构纳米颗粒保存在液体中或者以粉末形式进行保存。Further, the black product in the reaction system, namely the gold nickel sulfide core-shell structure nano-electrocatalyst, is extracted and purified, and the product is collected. Specifically, universal methods such as ultrasound, centrifugation, and filtration can be used for cleaning, and the gold-nickel sulfide core-shell structure nanoparticles are stored in a liquid or in a powder form.
得到的金硫化镍核壳结构纳米电催化剂为核壳结构，其中，所述内核为金核，所述外壳为硫化镍。所述金硫化镍核壳结构纳米电催化剂的整体尺寸即粒径范围为18-32nm。The obtained gold-nickel sulfide core-shell structure nano-electrocatalyst has a core-shell structure, wherein the core is a gold core and the shell is nickel sulfide. The overall size of the gold-nickel sulfide nano-electrocatalyst with a core-shell structure, that is, a particle size range is 18-32 nm.
下面结合具体实施例进行说明。The following describes it with reference to specific embodiments.
实施例1Example 1
一种电催化剂的制备方法，所述电催化剂为金硫化镍核壳结构纳米电催化剂，所述金硫化镍核壳结构纳米电催化剂包括内核和包覆在所述内核表面的壳层，其中，所述内核为金核，所述外壳为硫化镍；所述金硫化镍核壳结构纳米电催化剂的制备方法，包括以下步骤：A method for preparing an electrocatalyst, wherein the electrocatalyst is a gold-nickel sulfide core-shell structure nano-electrocatalyst, and the gold-nickel sulfide core-shell structure nano-electrocatalyst includes a core and a shell layer covering a surface of the core, wherein, The inner core is a gold core, and the outer shell is nickel sulfide; a method for preparing the gold-nickel sulfide core-shell structure nano-electrocatalyst includes the following steps:
S11.称量0.04克的氯金酸HAuCl4·xH2O，加入到10毫升油胺C18H37N纯度大于百分之二十的溶液中，持续进行磁力搅拌，直到形成金与油胺配位的前驱体；在惰性气氛（氩气气流速度为10ml/s）下，加热混合溶液到120℃，反应0.5小时（第一加热反应）；S11. Weigh 0.04 grams of chloroauric acid HAuCl4 · xH2O, add it to 10 ml of oleylamine C18H37N with a purity greater than 20%, and continue to magnetically stir until a precursor complexed with gold and oleylamine is formed; Under an inert atmosphere (the argon gas flow rate is 10 ml / s), heat the mixed solution to 120 ° C and react for 0.5 hours (first heating reaction);
S12.将经所述第一加热反应后的反应体系降温处理至温度低于25℃后，加入4毫摩尔的乙酰丙酮镍，140℃条件下持续搅拌0.5小时；在惰性气氛气流速度为10 ml/s的条件下，加热混合溶液到220℃，反应1小时（第二加热反应）；S12. After the reaction system after the first heating reaction is cooled down to a temperature lower than 25 ° C, 4 mmol of nickel acetylacetonate is added, and the stirring is continued for 0.5 hours at 140 ° C; the air flow speed is 10 ml in an inert atmosphere. / s, heating the mixed solution to 220 ° C, and reacting for 1 hour (second heating reaction);
S13.将经所述第二加热反应后的反应体系降温处理至温度低于25℃后，加入加入10毫摩尔正十二硫醇，80℃条件下持续搅拌0.5小时；在惰性气氛气流速度为10 ml/s的条件下，加热混合溶液到220℃，反应0.5小时，将溶液降温到25℃。S13. After the reaction system after the second heating reaction is cooled down to a temperature lower than 25 ° C, 10 mmol of n-dodecyl mercaptan is added, and the stirring is continued for 0.5 hours at 80 ° C; Under the condition of 10 ml / s, the mixed solution was heated to 220 ° C, and the reaction was performed for 0.5 hours, and the solution was cooled to 25 ° C.
S14.将40 毫升异丙醇倒入反应液中，充分搅拌，通过超声、离心反复洗涤5次。之后使用1:1 体积比的正己烷和乙醇混合溶液再次超声离心洗涤2 次，最后样品用乙醇分散保存。整个洗涤过程中，超声频率为100kHz，时间为5 分钟，离心速度为10000转每秒，离心时间为3 分钟。S14. Pour 40 ml of isopropanol into the reaction solution, stir thoroughly, and repeat washing 5 times by ultrasonic and centrifugation. After that, a mixed solution of n-hexane and ethanol was used in a 1: 1 volume ratio to perform ultrasonic centrifugal washing twice, and finally the sample was dispersed and stored in ethanol. During the entire washing process, the ultrasonic frequency was 100 kHz, the time was 5 minutes, the centrifugation speed was 10,000 rpm, and the centrifugation time was 3 minutes.
S15.将步骤S14所得产物分散液置于鼓风干燥箱中干燥12小时，得到产物粉末即为目标产物。S15. The product dispersion obtained in step S14 is dried in a blast drying box for 12 hours, and the product powder is the target product.
本发明实施例1制备得到的金硫化镍核壳结构纳米颗粒，整体物质构成如X射线衍射（附图1）所示；整体尺寸18~32纳米，为核壳构型，其中金为内核，壳层为硫化镍，核与壳之间含有空洞，形貌具体构型如扫描透射电子显微镜表征图（如附图2）所示。The gold-nickel sulfide core-shell structure nanoparticles prepared in Example 1 of the present invention have an overall material structure as shown in X-ray diffraction (Fig. 1); the overall size is 18 to 32 nanometers, and the core-shell configuration is in which gold is the core. The shell layer is nickel sulfide, and there are voids between the core and the shell. The specific configuration of the morphology is shown in the scanning transmission electron microscope (Figure 2).
将实施例1制备得到的金硫化镍核壳结构纳米颗粒剂催化碱性电解水分解实验中，在0.53伏特其单位活性质量能够达到256 安培每克催化剂，如电化学测试结果（附图3）所示；耐久性实验中，施加电压为0.5~1.2伏特，电压扫描速度为0.002伏特每秒，经过两万个循环，其单位活性质量仍然能达到250安培每克催化剂。In the experiment of catalyzing alkaline electrolytic water decomposition using the gold-nickel sulfide core-shell structure nanoparticles prepared in Example 1, its unit active mass can reach 256 amps per gram of catalyst at 0.53 volts, such as the results of electrochemical tests (Figure 3) As shown in the durability test, the applied voltage is 0.5 ~ 1.2 volts, the voltage scanning speed is 0.002 volts per second, and after 20,000 cycles, the unit active mass can still reach 250 amps per gram of catalyst.
其中，金硫化镍核壳结构纳米颗粒剂催化碱性电解水分解实验采用常规方法进行，具体的：取一定浓度的电催化剂分散液（1-10 mg/mL），滴在玻碳电极表面（3-6 mm直径），自然干燥，而后选取三电极***，在1mol/L的 KOH溶液中测试。Among them, the gold-nickel sulfide core-shell structure nanoparticle agent catalyzed the alkaline electrolytic water decomposition experiment using conventional methods, specifically: taking a certain concentration of the electrocatalyst dispersion liquid (1-10 mg / mL), dropped on the surface of the glassy carbon electrode (3-6 mm diameter), dried naturally, and then a three-electrode system was selected and tested in a 1 mol / L KOH solution.
以上所述实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围，均应包含在本发明的保护范围之内。The above-mentioned embodiments are only used to illustrate the technical solutions of the present invention, but are not limited thereto. Although the present invention is described in detail with reference to the foregoing embodiments, those skilled in the art should understand that they can still implement the foregoing implementations. The technical solutions described in the examples are modified, or some of the technical features are equivalently replaced; and these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention, and should be included in Within the scope of the present invention.

Claims (15)

  1. 一种电催化剂的制备方法，其特征在于，所述电催化剂为金硫化镍核壳结构纳米电催化剂，所述金硫化镍核壳结构纳米电催化剂包括内核和包覆在所述内核表面的壳层，其中，所述内核为金核，所述外壳为硫化镍；所述金硫化镍核壳结构纳米电催化剂的制备方法，包括以下步骤：A method for preparing an electrocatalyst, characterized in that the electrocatalyst is a gold-nickel sulfide core-shell structure nano-electrocatalyst, and the gold-nickel sulfide core-shell structure nano-electrocatalyst includes a core and a shell covering a surface of the core. Layer, wherein the core is a gold core and the outer shell is nickel sulfide; a method for preparing the gold nickel sulfide core-shell structure nano-electrocatalyst includes the following steps:
    提供金源，将所述金源溶于配体溶液中，混合处理形成金与配体的前驱体溶液；在惰性气氛下，将所述前驱体溶液进行第一加热反应；Providing a gold source, dissolving the gold source in a ligand solution, and mixing and forming a precursor solution of gold and the ligand; under a inert atmosphere, subjecting the precursor solution to a first heating reaction;
    将经所述第一加热反应后的反应体系降温处理至温度低于120℃后，加入镍盐，混合后得到第一混合溶液；在惰性气氛下，将所述第一混合溶液进行第二加热反应；After cooling the reaction system after the first heating reaction to a temperature lower than 120 ° C, adding a nickel salt and mixing to obtain a first mixed solution; under an inert atmosphere, heating the first mixed solution for a second time reaction;
    将经所述第二加热反应后的反应体系降温处理至温度低于120℃后，加入硫源，混合后得到第二混合溶液；在惰性气氛下，将所述第二混合溶液进行第三加热反应，经提取纯化处理，得到金硫化镍核壳结构纳米电催化剂。After cooling the reaction system after the second heating reaction to a temperature lower than 120 ° C, a sulfur source is added and mixed to obtain a second mixed solution; the second mixed solution is subjected to a third heating under an inert atmosphere. The reaction is subjected to extraction and purification treatment to obtain a gold nickel sulfide core-shell structure nano-electrocatalyst.
  2. 如权利要求1所述的电催化剂的制备方法，其特征在于，所述第一加热反应的温度为120-200℃，反应时间为0.01-5小时。The method of claim 1, wherein the temperature of the first heating reaction is 120-200 ° C, and the reaction time is 0.01-5 hours.
  3. 如权利要求1所述的电催化剂的制备方法，其特征在于，所述第二加热反应的温度为220-350℃，反应时间为0.1-5小时。The method for preparing an electrocatalyst according to claim 1, wherein the temperature of the second heating reaction is 220-350 ° C, and the reaction time is 0.1-5 hours.
  4. 如权利要求1所述的电催化剂的制备方法，其特征在于，所述第三加热反应的温度为220-250℃，反应时间为0.1-2小时。The method for preparing an electrocatalyst according to claim 1, wherein a temperature of the third heating reaction is 220-250 ° C, and a reaction time is 0.1-2 hours.
  5. 如权利要求1-4任一项所述的电催化剂的制备方法，其特征在于，所述配体溶液中的配体为油胺，且所述油胺在所述配体溶液中的质量百分含量大于20%。The method for preparing an electrocatalyst according to any one of claims 1 to 4, wherein the ligand in the ligand solution is oleylamine, and the mass percentage of the oleylamine in the ligand solution is 100%. The content is more than 20%.
  6. 如权利要求1-4任一项所述的电催化剂的制备方法，其特征在于，将经所述第一加热反应后的反应体系降温处理至温度低于120℃后，加入镍盐，混合后得到第一混合溶液的步骤中，在加入所述镍盐后，加入硼烷基有机化合物，混合后得到第一混合溶液；或The method for preparing an electrocatalyst according to any one of claims 1 to 4, characterized in that, after the reaction system after the first heating reaction is cooled down to a temperature lower than 120 ° C, a nickel salt is added and mixed In the step of obtaining the first mixed solution, after the nickel salt is added, a boryl organic compound is added, and the first mixed solution is obtained after mixing; or
    将经所述第一加热反应后的反应体系降温处理至温度低于120℃后，加入镍盐，混合后得到第一混合溶液的步骤中，在加入所述镍盐后，加入表面活性剂，混合后得到第一混合溶液；或In the step of cooling the reaction system after the first heating reaction to a temperature lower than 120 ° C, adding a nickel salt, and mixing to obtain a first mixed solution, adding a surfactant after adding the nickel salt, Obtain a first mixed solution after mixing; or
    将经所述第一加热反应后的反应体系降温处理至温度低于120℃后，加入镍盐，混合后得到第一混合溶液的步骤中，在加入所述镍盐后，加入硼烷基有机化合物和表面活性剂，混合后得到第一混合溶液。In the step of cooling the reaction system after the first heating reaction to a temperature lower than 120 ° C., adding a nickel salt to obtain a first mixed solution after mixing, after adding the nickel salt, adding a boryl organic The compound and the surfactant are mixed to obtain a first mixed solution.
  7. 如权利要求6所述的电催化剂的制备方法，其特征在于，当添加有所述硼烷基有机化合物时，所述硼烷基有机化合物选自硼烷氨、叔丁基烷胺中的至少一种。The method for preparing an electrocatalyst according to claim 6, characterized in that, when the boryl organic compound is added, the boralkyl organic compound is selected from at least one of borane ammonia and tert-butyl alkylamine. One.
  8. 如权利要求7所述的电催化剂的制备方法，其特征在于，所述硼烷基有机化合物与金的摩尔比为5:1-40:1。The method for preparing an electrocatalyst according to claim 7, wherein a molar ratio of the boryl organic compound to gold is 5: 1 to 40: 1.
  9. 如权利要求6所述的电催化剂的制备方法，其特征在于，当添加有所述表面活性剂时，所述表面活性剂选自油酸、三辛基氧化膦、三辛基膦中的至少一种。The method for preparing an electrocatalyst according to claim 6, wherein, when the surfactant is added, the surfactant is selected from at least oleic acid, trioctylphosphine oxide, and trioctylphosphine. One.
  10. 如权利要求9所述的电催化剂的制备方法，其特征在于，所述表面活性剂与金的摩尔比为2:1-100:1。The method for preparing an electrocatalyst according to claim 9, wherein a molar ratio of the surfactant to gold is 2: 1 to 100: 1.
  11. 如权利要求1-4任一项所述的电催化剂的制备方法，其特征在于，所述金源、所述镍盐、所述硫源的添加量满足：The method for preparing an electrocatalyst according to any one of claims 1 to 4, wherein the addition amount of the gold source, the nickel salt, and the sulfur source satisfies:
    金与镍的摩尔比为0.1-20：1；The molar ratio of gold to nickel is 0.1-20: 1;
    镍与硫的摩尔比为1:1.5-20。The molar ratio of nickel to sulfur is 1: 1.5-20.
  12. 如权利要求1-4任一项所述的电催化剂的制备方法，其特征在于，所述前驱体溶液中，金离子的摩尔浓度为0.01-20mmol/L。The method for preparing an electrocatalyst according to any one of claims 1 to 4, wherein the molar concentration of gold ions in the precursor solution is 0.01-20 mmol / L.
  13. 如权利要求1-4任一项所述的电催化剂的制备方法，其特征在于，所述第一混合溶液中，镍离子的摩尔浓度为50-300mmol/L。The method for preparing an electrocatalyst according to any one of claims 1 to 4, wherein the molar concentration of nickel ions in the first mixed solution is 50-300 mmol / L.
  14. 一种电催化剂，其特征在于，所述电催化剂为金硫化镍核壳结构纳米电催化剂，所述金硫化镍核壳结构纳米电催化剂包括内核和包覆在所述内核表面的壳层，其中，所述内核为金核，所述外壳为硫化镍，且所述金核由纳米金颗粒组成。An electrocatalyst, characterized in that the electrocatalyst is a gold-nickel sulfide core-shell structure nano-electrocatalyst, and the gold-nickel sulfide core-shell structure nano-electrocatalyst includes a core and a shell layer covering a surface of the core, wherein The core is a gold core, the shell is nickel sulfide, and the gold core is composed of nano-gold particles.
  15. 如权利要求14所述的电催化剂，其特征在于，所述所述金硫化镍核壳结构纳米电催化剂的粒径为18-32nm，其中，所述纳米金颗粒的粒径尺寸为6-10nm，所述壳层的厚度为0.2-8nm。The electrocatalyst according to claim 14, wherein the particle size of the gold-nickel sulfide core-shell nano-electrocatalyst is 18-32nm, and the particle size of the nano-gold particles is 6-10nm. The thickness of the shell layer is 0.2-8 nm.
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