CN114232026A - Nitrogen-doped carbon-coated Ni3P/Ni heterostructure nanoparticle electrocatalyst and preparation method and application thereof - Google Patents

Nitrogen-doped carbon-coated Ni3P/Ni heterostructure nanoparticle electrocatalyst and preparation method and application thereof Download PDF

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CN114232026A
CN114232026A CN202111532104.3A CN202111532104A CN114232026A CN 114232026 A CN114232026 A CN 114232026A CN 202111532104 A CN202111532104 A CN 202111532104A CN 114232026 A CN114232026 A CN 114232026A
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nitrogen
heterostructure
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doped carbon
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冯亮亮
付常乐
黄剑锋
冯永强
曹丽云
李东明
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • 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

Abstract

The invention discloses nitrogen-doped carbon-coated Ni3The preparation method comprises the steps of adopting insoluble nickel salt as a precursor, uniformly mixing an insoluble nickel source and a nitrogen-containing carbon source, adding a sodium hypophosphite phosphorus source, placing the mixture in an inert atmosphere for high-temperature calcination, and carrying out in-situ carbonization-phosphorization reaction by using a gas-phase phosphorization method to realize the nitrogen doping of nano-particlesCarbon coated Ni3And preparing a P/Ni heterostructure. The obtained material is uniformly dispersed, has metalloid conductivity, has larger electrochemical specific surface area and excellent chemical stability, can be used as a hydrogen production catalyst material for electrocatalytic water decomposition, and can reach 10mA/cm only by an overpotential of 70mV2The current density of (1). Meanwhile, the preparation method is simple and convenient, can be obtained only by high-temperature heat treatment, has easily controlled reaction conditions, and has the characteristics of industrial batch production.

Description

Nitrogen-doped carbon-coated Ni3P/Ni heterostructure nanoparticle electrocatalyst and preparation method and application thereof
Technical Field
The invention relates to the field of electrocatalyst materials, in particular to nitrogen-doped carbon-coated Ni3P/Ni heterostructure nanoparticle electrocatalyst, preparation method and application thereof.
Background
Hydrogen energy is considered to be an ideal substitute for traditional fossil energy (such as coal, petroleum, natural gas and the like) due to its characteristics of cleanness, high efficiency, sustainability and the like, and has become a hot spot of global research. In a plurality of hydrogen energy development technologies, the hydrogen production by water electrolysis has no pollution, the product purity is high, the process is simple, and even the electric energy converted by 'water abandoning, wind abandoning and light abandoning' can be fully utilized to realize the development of sustainable hydrogen economy. At present, the biggest challenge of hydrogen production by water electrolysis is high energy consumption, and an electrocatalyst is used to effectively reduce a chemical barrier in reaction so as to greatly improve the hydrogen production rate. However, the noble metal platinum-based catalyst with the most excellent hydrogen production performance has high cost and poor durability, which limits the large-scale application of the noble metal platinum-based catalyst in practical industrial production, so that the design and development of a non-noble metal catalyst with low price, high efficiency, excellent stability and excellent catalytic activity become a great challenge.
The transition metal phosphide not only has an electronic structure similar to that of metal and long-term chemical stability, but also has good catalytic activity in the hydrogen production process because phosphorus and metal sites can be respectively used as a proton receiving site and a hydride receiving site, and is favored by researchers. Nickel (Ni) phosphidexPy) Is one of the most promising candidate compounds in transition metal phosphides, where Ni3P as the most nickel-rich compound contains rich Ni-Ni bonds andthe Ni-P bond has the characteristics of metal and even superconductivity, and the metal-phosphorus bond with strong covalent property can greatly improve the chemical stability, thereby having potential development prospect in the field of electrocatalysis. However, in the reported studies, Ni3The performance of P under the alkaline condition is relatively poor, and the popularization of P in practical application is hindered. And constructing a heterostructure or compositing with a carbon material substrate as an effective strategy to optimize Ni3The electron structure and chemical stability of P are used to further improve the exposure of the catalytic active sites and the electrocatalytic activity of the material, and based on the result, Ni is prepared by designing a high-efficiency simple synthetic route3P electrocatalysts have become a great challenge.
Synthesis of Ni in general3The P condition is very harsh, and the preparation process is complicated, so that the related Ni3The preparation and application of P are reported, and Ni is prepared by a low-cost, high-yield and environment-friendly method3P remains challenging. Related technology adopts liquid phase reduction method to prepare Ni3P is applied to phenol hydrodeoxygenation, wherein strict reaction pH needs to be controlled, and calcination is carried out in a hydrogen atmosphere. In addition, the eggshell structure Ni synthesized by the related art3The P is used as an electrode material of the super capacitor, the preparation process is complex and tedious, the period is long, the cost is high, and the practical application development of the material is not facilitated.
Disclosure of Invention
In order to solve the problems of complex preparation and difficult process in the prior art, the invention provides nitrogen-doped carbon-coated Ni3The P/Ni heterostructure nanoparticle electrocatalyst, the preparation method and the application thereof adopt a simple hydrothermal method combined with an in-situ carbonization and phosphorization strategy, the raw materials are simple, the process is easy to control, and the obtained product can exert high-efficiency electrocatalytic hydrogen production activity so as to promote the development of the practical application of the water-cracking electrocatalyst.
In order to achieve the purpose, the invention provides nitrogen-doped carbon-coated Ni3The preparation method of the P/Ni heterostructure nanoparticle electrocatalyst comprises the following steps:
the method comprises the following steps: weighing 0.13-0.17 g of insoluble nickel source and 0.22-0.28 g of nitrogen-containing carbon source, grinding and mixing, weighing 0.45-0.55 g of sodium hypophosphite, and respectively placing the insoluble nickel source, the nitrogen-containing carbon source and the sodium hypophosphite into a reactor, wherein the insoluble nickel source and the nitrogen-containing carbon source are positioned on one side of the sodium hypophosphite;
step two: carrying out high-temperature vacuum calcination reaction on a reactor filled with an insoluble nickel source, a nitrogen-containing carbon source and sodium hypophosphite in an inert atmosphere, wherein the sodium hypophosphite is positioned at the upstream position of the gas source, the reaction temperature is 650-850 ℃, and the temperature is kept for 1-3 hours, so that the nitrogen-doped carbon-coated Ni is obtained3P/Ni heterostructure nanoparticle electrocatalysts.
Preferably, the insoluble nickel source in step 1) is any one or more of nickel oxalate, nickel hydroxide and nickel oxide.
Preferably, the nitrogen-containing carbon source in step 1) is any one of melamine, dicyandiamide, glucose and polyaniline.
Preferably, the insoluble nickel source and the nitrogen-containing carbon source in the step 1) are mechanically ground and mixed, and then transferred to a small porcelain boat, sodium hypophosphite is placed at one end of a large porcelain boat, and the small porcelain boat is sleeved in the large porcelain boat and placed at the other end of the large porcelain boat.
Preferably, the small porcelain boat and the large porcelain boat in the step 2) are placed in a high-temperature vacuum tube furnace for high-temperature vacuum calcination reaction, one end of the large porcelain boat, which is provided with the phosphorus source, is located at the upstream position of the gas source, and the small porcelain boat is located at the downstream position.
Preferably, the heating rate of the calcination in the step 2) is 8-12 ℃/min.
Preferably, the inert atmosphere in the step 2) is argon atmosphere, and the introduction flow rate is 900-1100 sccm.
The invention also provides nitrogen-doped carbon-coated Ni3The P/Ni heterostructure nanoparticle electrocatalyst adopts the nitrogen-doped carbon coated Ni3The P/Ni heterostructure nanoparticle electrocatalyst is prepared by a preparation method, and Ni in the electrocatalyst3Both P and Ni are present in the form of nanoparticles and combine with each other to form a heterostructure.
Preferably, the size of the nano particles is 10-50 nm.
The invention also provides the nitrogen-doped carbon-coated Ni3The application of P/Ni heterostructure nanoparticle electrocatalyst as alkaline hydrogen production catalyst for electrocatalytic water cracking reaches 10mA/cm under over potential of 70mV2The current density of (1).
Compared with the prior art, the invention has the following beneficial effects:
1) the method adopts an in-situ carbonization and phosphorization method to prepare the synthetic product, has the advantages of easily obtained raw materials, simple and convenient method, easily controlled process, low cost, convenient quantitative production and no need of large-scale equipment and harsh reaction conditions.
2) The nitrogen-containing carbon source added in the invention can be used as a reducing agent to promote Ni3P is generated, a nitrogen-doped carbon-coated structure can be formed, the carbon coating can improve the conductivity of the whole material and more active sites, and the electrocatalyst is protected from the corrosion of electrolyte so as to maintain excellent catalytic activity and stability.
3) The product prepared in the invention is in the form of nano particles, and a large amount of Ni is formed between the particles3The P/Ni heterostructure has rich heterogeneous interfaces which can regulate and control the electronic state, thereby accelerating the transfer and mass transfer of charges; the carbon coating structure can avoid self-aggregation of metal particles under high-temperature conditions, can confine metal nanoparticles in the carbon layer, and has excellent performance when being used as a hydrogen production catalyst for electrolysis.
4) In the invention, the Ni in the reaction is realized by strictly controlling the condition parameters such as the amount of the carbon-containing source, the amount of the phosphorus source, the calcining temperature, the calcining time and the like3P, Ni, and the control of the thickness of the nitrogen-doped carbon layer, fully utilizes the reduction effect and the unique space confinement effect of the carbon source, and finally realizes the coating of Ni by the nitrogen-doped carbon3Controllable synthesis of P/Ni heterostructure nanoparticle electrocatalysts.
5) The insoluble nickel source is used as a precursor to coat the nitrogen-doped carbon with Ni3The synthesis of P/Ni heterostructure nanoparticle electrocatalyst plays a key role, when nickel-containing precursor is replaced by hexahydrate with equal amount of substancesWhen nickel chloride is synthesized as a nickel source, carbon-coated Ni/Ni having the phase cannot be synthesized3P nanoparticle composites.
6) The nitrogen-doped carbon-coated Ni prepared by the invention3P/Ni heterostructure nanoparticle electrocatalyst, the nanometer particle degree of crystallinity is high, the appearance is unanimous, size highly dispersed, and the nanometer particle size is 10 ~ 50nm, and generally formed heterostructure, show surface effect, the quantum size effect that bulk material or small molecule material do not possess, and heterostructure owned abundant heterogeneous interface, can regulate and control electronic state and structure to accelerate the conductivity, promote material intrinsic activity, this structure possesses apparent advantage in electrocatalysis hydrogen field.
Drawings
FIG. 1 shows N-doped carbon-coated Ni prepared in example 1 of the present invention3XRD pattern of P/Ni heterostructure nanoparticle electrocatalyst;
FIG. 2 shows N-doped carbon-coated Ni prepared in example 1 of the present invention3SEM spectra of P/Ni heterostructure nanoparticle electrocatalysts;
FIG. 3 shows N-doped carbon-coated Ni prepared in example 1 of the present invention3TEM spectra of P/Ni heterostructure nanoparticle electrocatalysts;
FIG. 4 shows N-doped carbon-coated Ni prepared in example 1 of the present invention3HRTEM spectrum of P/Ni heterostructure nanoparticle electrocatalyst;
FIG. 5 shows N-doped carbon-coated Ni prepared in example 1 of the present invention3An element distribution map of the P/Ni heterostructure nanoparticle electrocatalyst;
FIG. 6 shows N-doped carbon-coated Ni prepared in example 1 of the present invention3LSV hydrogen production performance curve of P/Ni heterostructure nanoparticle electrocatalyst.
Figure 7 is an XRD pattern of an electrocatalyst prepared in example 1 of the present invention replacing the nickel-containing precursor with nickel chloride hexahydrate.
Fig. 8 is an SEM image of an electrocatalyst prepared by replacing a nickel-containing precursor with nickel chloride hexahydrate in example 1 of the present invention.
Fig. 9 is an XRD pattern of the electrocatalyst prepared in example 1 of the present invention without adding dicyandiamide as the nitrogen-containing carbon source.
Figure 10 is an XRD pattern of an electrocatalyst prepared in example 1 of the present invention without the addition of a phosphorus source.
Detailed Description
The present invention will be further explained with reference to the drawings and specific examples in the specification, and it should be understood that the examples described are only a part of the examples of the present application, and not all examples. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The invention provides nitrogen-doped carbon-coated Ni3The preparation method of the P/Ni heterostructure nanoparticle electrocatalyst specifically comprises the following steps:
the method comprises the following steps: weighing 0.13-0.17 g of insoluble nickel source and 0.22-0.28 g of nitrogen-containing carbon source, mechanically grinding and mixing in a mortar, transferring to a small porcelain boat, weighing 0.45-0.55 g of sodium hypophosphite, placing at one end of a large porcelain boat, sleeving the small porcelain boat into the large porcelain boat, and placing at the other end of the large porcelain boat; the insoluble nickel salt is any one or more of nickel oxalate, nickel hydroxide and nickel oxide; the nitrogen-containing carbon source is any one of melamine, dicyanodiamine, glucose and polyaniline;
step two: placing the large porcelain boat and the small porcelain boat into a high-temperature vacuum tube furnace, wherein one end of the large porcelain boat, which is provided with a phosphorus source, is positioned at the upstream position of a gas source, the small porcelain boat is placed at the downstream position of the tube furnace and is placed in inert atmosphere such as argon, the calcining heating rate is 8-12 ℃/min, the introducing flow of the argon atmosphere is 900-1100 sccm, the reaction temperature is 650-850 ℃, and the heat preservation is carried out for 1-3 hours, so that the nitrogen-doped carbon-coated Ni is obtained3P/Ni heterostructure nanoparticle electrocatalysts.
The invention also provides nitrogen-doped carbon-coated Ni prepared by the preparation method3P/Ni heterostructure nanoparticle electrocatalyst of nitrogen doped carbon coated Ni3Ni in P/Ni heterostructure nanoparticle electrocatalyst3Both P and Ni are present in the form of nanoparticles,and the nano particles are combined with each other to form a heterostructure, and the size of the nano particles is 10-50 nm. The invention also provides the nitrogen-doped carbon-coated Ni3Application of P/Ni heterostructure nanoparticle electrocatalyst as alkaline hydrogen production catalyst for electrocatalytic water cracking, and overpotential of 70mV is only needed to reach 10mA/cm2The current density of (1).
According to the invention, an insoluble nickel salt is used as a precursor, and a nitrogen-containing carbon source and a sodium hypophosphite phosphorus source are subjected to in-situ carbonization-phosphorization reaction in an inert atmosphere to obtain the electrocatalyst material. Uniformly mixing an insoluble nickel source and a carbon source, adding a phosphorus source, placing the mixture in an argon atmosphere for high-temperature calcination, and carrying out a phosphating reaction by using a gas-phase phosphating method to realize the coating of Ni on the nano-granular nitrogen-doped carbon3And preparing a P/Ni heterostructure. The obtained material is uniformly dispersed, has metalloid conductivity, has larger electrochemical specific surface area and excellent chemical stability, can be used as a hydrogen production catalyst material for electrocatalytic water decomposition, and can reach 10mA/cm only by an overpotential of 70mV2The current density of (1). Meanwhile, the preparation method is simple and convenient, can be obtained only by high-temperature heat treatment, has easily controlled reaction conditions, and has the characteristics of industrial batch production.
The present invention will be explained in detail with reference to specific examples.
Example 1:
the method comprises the following steps: weighing 0.16g of nickel oxalate and 0.24g of dicyanodiamide, mechanically grinding and mixing in a mortar, transferring to a small porcelain boat, then weighing 0.55g of sodium hypophosphite, placing at one end of a large porcelain boat, sleeving the small porcelain boat into the large porcelain boat, and placing at the other end;
step two: placing the large and small porcelain boats into a high-temperature vacuum tube furnace, placing the high-temperature vacuum tube furnace in argon atmosphere, keeping the reaction temperature at 750 ℃ for 2 hours, heating the calcination at a speed of 10 ℃/min, and introducing the argon atmosphere with a flow of 900sccm to obtain the nitrogen-doped carbon-coated Ni3P/Ni heterostructure nanoparticle electrocatalyst materials.
It can be seen from FIG. 1 that the characteristic peaks corresponding to Ni at 44.6 °, 51.9 °, and 76.5 °, while Ni at 36.3 °, 41.7 °, 42.8 °, 45.2 °, 46.6 °, and 50.5 ° are shown3Characteristic peak of P, proving Ni3Successful fabrication of P/Ni heterostructures.
As is apparent from the powder surface in fig. 2, the electrocatalyst material is assembled from a plurality of nanoparticles.
As can be seen from the internal structure of the material in FIG. 3, the nano-particles are coated by the carbon layer, the size of the nano-particles is 10-50 nm, and a heterostructure is generally formed, which proves the formation of the carbon-coated structure.
As can be seen from FIGS. 4a and 4b, the lattice fringes at 0.176nm and 0.194nm in FIG. 4a correspond to the (200) plane of Ni and Ni, respectively3The (141) plane of P, the heterostructure in the diagram of FIG. 4b is Ni corresponding to a lattice fringe of 0.216nm3P (141) plane and Ni (203) plane corresponding to 0.203nm lattice fringe, and it was confirmed that Ni was coated with carbon3Successful preparation of P/Ni heterostructure nanoparticle electrocatalysts.
As can be seen from the elemental distribution diagram of FIG. 5, Ni and P elements are mainly distributed in the region where the nanoparticles are located, and C and N elements are uniformly distributed over the entire region, thereby proving the nitrogen-doped carbon cladding structure and Ni3P/Ni heterostructure nanoparticles are present.
It can be seen from FIG. 6 that the catalyst exhibits excellent electrocatalytic activity under alkaline conditions (pH 14), requiring only 70mV overpotential to reach 10mA/cm2The current density of (1).
In example 1, nickel-containing precursor, namely nickel oxalate was replaced by nickel chloride hexahydrate, and the XRD pattern of the prepared electrocatalyst is shown in fig. 7, and as can be seen from fig. 7, the nickel-containing precursor was directly replaced by nickel chloride hexahydrate, and the phase of the prepared material was complex and contained Ni and Ni3P、Ni8P3Three phases, and the target product cannot be prepared.
In example 1, the nickel-containing precursor, i.e., nickel oxalate, is replaced by nickel chloride hexahydrate, and the SEM spectrum of the prepared electrocatalyst is shown in fig. 8, and it can be seen from fig. 8 that when the nickel-containing precursor is directly replaced by nickel chloride hexahydrate, the structure of the nickel-containing precursor presents a random cross-linked structure, which prevents the exposure of active sites, and thus the catalytic performance of the expected structure cannot be obtained, and thus the importance of the nickel-containing precursor can be obtained.
The XRD pattern of the electrocatalyst prepared in example 1 without dicyandiamide, i.e. without dicyanodiamide as nitrogen-containing carbon source, is shown in FIG. 9. it can be seen from FIG. 9 that Ni is present in addition to the three distinct characteristic peaks of Ni3P (PDF #65-1605) and Ni2.55P (PDF #18-0884) two-phase nickel phosphide compound in the absence of nitrogen-containing carbon source as part of the reducing agent to form Ni3P, it can thus be seen that the nitrogen-containing carbon source can provide both a carbon substrate and an important role as a reducing agent in this synthesis system.
The XRD pattern of the electrocatalyst prepared in example 1 without adding a phosphorus source, i.e. without adding sodium hypophosphite, is shown in fig. 10, and it can be seen from fig. 10 that only three characteristic peaks of Ni are shown at 44.6 °, 51.9 °, and 76.5 °, indicating that the addition of a carbon source has a significant reducing effect, while the phosphorus source plays a key role in the formation of phosphide.
Example 2:
the method comprises the following steps: weighing 0.17g of nickel hydroxide and 0.28g of melamine, mechanically grinding and mixing in a mortar, transferring to a small porcelain boat, then weighing 0.45g of sodium hypophosphite at one end of a large porcelain boat, sleeving the small porcelain boat into the large porcelain boat, and placing at the other end of the large porcelain boat;
step two: placing the large and small porcelain boats into a high-temperature vacuum tube furnace, placing the high-temperature vacuum tube furnace in an argon atmosphere, keeping the reaction temperature at 750 ℃ for 3 hours, heating the calcination at a speed of 12 ℃/min, and introducing the argon atmosphere with a flow of 1100sccm to obtain the nitrogen-doped carbon-coated Ni3P/Ni heterostructure nanoparticle electrocatalyst materials.
Example 3:
the method comprises the following steps: weighing 0.15g of nickel oxide and 0.24g of glucose, mechanically grinding and mixing in a mortar, transferring to a small porcelain boat, weighing 0.5g of sodium hypophosphite at one end of a large porcelain boat, sleeving the small porcelain boat into the large porcelain boat, and placing at the other end of the large porcelain boat;
step two: placing the porcelain boats into a high-temperature vacuum tube furnace, placing the furnace in argon atmosphere, keeping the temperature for 2 hours at 650 ℃, and heating at a high speed during calcinationThe rate is 8 ℃/min, the flow of argon gas is introduced into the atmosphere of 1000sccm, and the nitrogen-doped carbon-coated Ni is obtained3P/Ni heterostructure nanoparticle electrocatalyst materials.
Example 4:
the method comprises the following steps: weighing 0.13g of nickel oxalate and 0.25g of dicyanodiamide, mechanically grinding and mixing in a mortar, transferring to a small porcelain boat, then weighing 0.45g of sodium hypophosphite, placing at one end of a large porcelain boat, sleeving the small porcelain boat into the large porcelain boat, and placing at the other end;
step two: placing the large and small porcelain boats into a high-temperature vacuum tube furnace, placing the high-temperature vacuum tube furnace in an argon atmosphere, keeping the reaction temperature at 750 ℃ for 3 hours, heating the calcination at a speed of 10 ℃/min, and introducing the argon atmosphere with a flow of 1000sccm to obtain the nitrogen-doped carbon-coated Ni3P/Ni heterostructure nanoparticle electrocatalyst materials.
Example 5:
the method comprises the following steps: weighing 0.15g of nickel oxide and 0.28g of polyaniline, mechanically grinding and mixing in a mortar, transferring to a small porcelain boat, weighing 0.5g of sodium hypophosphite at one end of a large porcelain boat, sleeving the small porcelain boat into the large porcelain boat, and placing at the other end of the large porcelain boat;
step two: placing the large and small porcelain boats into a high-temperature vacuum tube furnace, placing the high-temperature vacuum tube furnace in an argon atmosphere, keeping the reaction temperature at 850 ℃ for 1h, heating the calcination at a speed of 10 ℃/min, and introducing argon into the furnace at a flow of 1100sccm to obtain the nitrogen-doped carbon-coated Ni3P/Ni heterostructure nanoparticle electrocatalyst materials.
Example 6:
the method comprises the following steps: weighing 0.14g of nickel hydroxide and 0.26g of dicyanodiamide, mechanically grinding and mixing in a mortar, transferring to a small porcelain boat, then weighing 0.55g of sodium hypophosphite, placing at one end of a large porcelain boat, sleeving the small porcelain boat into the large porcelain boat, and placing at the other end;
step two: placing the large and small porcelain boats into a high-temperature vacuum tube furnace, placing the high-temperature vacuum tube furnace in an argon atmosphere, keeping the reaction temperature at 800 ℃ for 2 hours, heating the calcination at a speed of 8 ℃/min, and introducing an argon atmosphere with a flow of 900sccm to obtain the nitrogen-doped carbon-coated Ni3P/Ni heterostructure nanoparticle electrocatalyst materials.
Example 7:
the method comprises the following steps: weighing 0.13g of nickel hydroxide and nickel oxide in any proportion and 0.22g of polyaniline, mechanically grinding and mixing in a mortar, transferring to a small porcelain boat, weighing 0.45g of sodium hypophosphite, placing at one end of a large porcelain boat, sleeving the small porcelain boat into the large porcelain boat, and placing at the other end;
step two: placing the large and small porcelain boats into a high-temperature vacuum tube furnace, wherein one end of the large porcelain boat, which is provided with a phosphorus source, is positioned at the upstream position of a gas source, the small porcelain boat is placed at the downstream position of the tube furnace and is placed in inert atmosphere such as argon, the calcining heating rate is 8 ℃/min, the flow of argon atmosphere is 900sccm, the reaction temperature is 650 ℃ and the temperature is kept for 1h, and then the nitrogen-doped carbon coated Ni is obtained3P/Ni heterostructure nanoparticle electrocatalysts.
Example 8:
the method comprises the following steps: weighing 0.17g of nickel oxalate and nickel oxide in any proportion and 0.28g of melamine, mechanically grinding and mixing in a mortar, transferring to a small porcelain boat, weighing 0.55g of sodium hypophosphite, placing at one end of a large porcelain boat, sleeving the small porcelain boat into the large porcelain boat, and placing at the other end of the large porcelain boat; the insoluble nickel salt is; adopting a nitrogen-containing carbon source;
step two: placing the large and small porcelain boats into a high-temperature vacuum tube furnace, wherein one end of the large porcelain boat, which is provided with a phosphorus source, is positioned at the upstream position of a gas source, the small porcelain boat is placed at the downstream position of the tube furnace and is placed in inert atmosphere such as argon, the calcining heating rate is 12 ℃/min, the flow of argon atmosphere is 1100sccm, the reaction temperature is 850 ℃ and the temperature is kept for 3 hours, thus obtaining the nitrogen-doped carbon coated Ni3P/Ni heterostructure nanoparticle electrocatalysts.
Example 9:
the method comprises the following steps: weighing 0.15g of nickel oxalate, nickel hydroxide and nickel oxide in any proportion and 0.25g of glucose, mechanically grinding and mixing in a mortar, transferring to a small porcelain boat, weighing 0.50g of sodium hypophosphite, placing at one end of a large porcelain boat, sleeving the small porcelain boat into the large porcelain boat, and placing at the other end;
step two: placing the large and small porcelain boats into a high-temperature vacuum tube furnace, wherein the large porcelain boat is filled with phosphorusOne end of the source is positioned at the upstream position of the gas source, the small porcelain boat is arranged at the downstream position of the tube furnace and is arranged in inert atmosphere such as argon, the calcining heating rate is 10 ℃/min, the flow of the argon atmosphere is 1000sccm, the reaction temperature is 750 ℃, and the temperature is kept for 2h, thus obtaining the nitrogen-doped carbon coated Ni3P/Ni heterostructure nanoparticle electrocatalysts.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. Nitrogen-doped carbon-coated Ni3The preparation method of the P/Ni heterostructure nanoparticle electrocatalyst is characterized by comprising the following steps of:
the method comprises the following steps: weighing 0.13-0.17 g of insoluble nickel source and 0.22-0.28 g of nitrogen-containing carbon source, grinding and mixing, weighing 0.45-0.55 g of sodium hypophosphite, and respectively placing the insoluble nickel source, the nitrogen-containing carbon source and the sodium hypophosphite into a reactor, wherein the insoluble nickel source and the nitrogen-containing carbon source are positioned on one side of the sodium hypophosphite;
step two: carrying out high-temperature vacuum calcination reaction on a reactor filled with an insoluble nickel source, a nitrogen-containing carbon source and sodium hypophosphite in an inert atmosphere, wherein the sodium hypophosphite is positioned at the upstream position of the gas source, the reaction temperature is 650-850 ℃, and the temperature is kept for 1-3 hours, so that the nitrogen-doped carbon-coated Ni is obtained3P/Ni heterostructure nanoparticle electrocatalysts.
2. The nitrogen-doped carbon-coated Ni as claimed in claim 13The preparation method of the P/Ni heterostructure nanoparticle electrocatalyst is characterized in that the insoluble nickel source in the step 1) is any one or more of nickel oxalate, nickel hydroxide and nickel oxide.
3. The nitrogen-doped carbon-coated Ni as claimed in claim 13The preparation method of the P/Ni heterostructure nanoparticle electrocatalyst is characterized in that the nitrogen-containing carbon source in the step 1) is any one of melamine, dicyanodiamine, glucose and polyaniline.
4. The nitrogen-doped carbon-coated Ni as claimed in claim 13The preparation method of the P/Ni heterostructure nanoparticle electrocatalyst is characterized in that in the step 1), an insoluble nickel source and a nitrogen-containing carbon source are mechanically ground and mixed and then transferred into a small porcelain boat, sodium hypophosphite is placed at one end of a large porcelain boat, and the small porcelain boat is sleeved into the large porcelain boat and placed at the other end of the large porcelain boat.
5. The N-doped carbon-coated Ni as claimed in claim 43The preparation method of the P/Ni heterostructure nanoparticle electrocatalyst is characterized in that the small porcelain boat and the large porcelain boat in the step 2) are placed in a high-temperature vacuum tube furnace to carry out high-temperature vacuum calcination reaction, one end of the large porcelain boat, which is provided with a phosphorus source, is positioned at the upstream position of a gas source, and the small porcelain boat is positioned at the downstream position.
6. The N-doped carbon-coated Ni as claimed in claim 53The preparation method of the P/Ni heterostructure nanoparticle electrocatalyst is characterized in that the calcination temperature rise rate in the step 2) is 8-12 ℃/min.
7. The N-doped carbon-coated Ni as claimed in claim 53The preparation method of the P/Ni heterostructure nanoparticle electrocatalyst is characterized in that the inert atmosphere in the step 2) is argon atmosphere, and the flow rate is 900-1100 sccm.
8. Nitrogen-doped carbon-coated Ni3P/Ni heterostructure nanoparticle electrocatalyst characterized in that Ni is coated with nitrogen doped carbon according to any one of claims 1 to 73P/The preparation method of the Ni heterostructure nanoparticle electrocatalyst is obtained by preparing the electrocatalyst, wherein Ni is contained in the electrocatalyst3Both P and Ni are present in the form of nanoparticles and combine with each other to form a heterostructure.
9. The N-doped carbon-coated Ni as claimed in claim 83The P/Ni heterostructure nanoparticle electrocatalyst is characterized in that the size of nanoparticles is 10-50 nm.
10. The nitrogen-doped carbon-coated Ni as claimed in claim 8 or 93The P/Ni heterostructure nanoparticle electrocatalyst is applied as an electrocatalytic water cracking alkaline hydrogen production catalyst.
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