CN115044933A - Ni 12 P 5 Or Ni 2 Preparation method and application of P nano array - Google Patents

Ni 12 P 5 Or Ni 2 Preparation method and application of P nano array Download PDF

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CN115044933A
CN115044933A CN202210498874.9A CN202210498874A CN115044933A CN 115044933 A CN115044933 A CN 115044933A CN 202210498874 A CN202210498874 A CN 202210498874A CN 115044933 A CN115044933 A CN 115044933A
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carrier
preparation
catalyst
tin
washing
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CN115044933B (en
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田新龙
封苏阳
李静
邓培林
罗俊明
沈义俊
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Hainan Deep Sea New Energy Technology Co ltd
Hainan University
Sanya Research Institute of Hainan University
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Hainan Deep Sea New Energy Technology Co ltd
Hainan University
Sanya Research Institute of Hainan University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061—Metal or alloy
    • 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
    • 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

Abstract

The invention discloses Ni 12 P 5 Or Ni 2 A preparation method of a P nano array relates to the technical field of catalyst preparation, and comprises the following steps: pretreatment of a carrier: removing oxides and organic impurities on the surface of a carrier, wherein the carrier is used for providing a nickel source and providing a space for in-situ growth for the nano array; preparation of Ni 12 P 5 Or Ni 2 P: covering phosphate on the pretreated carrier, heating to 250-350 ℃ in an inert atmosphere, preserving heat for 0.5-4h, washing and drying the obtained product to obtain Ni 12 P 5 Support or Ni 2 P/vector. Preparation of Ni by the method of the invention 12 P 5 Support or Ni 2 The P/carrier can obtain single phosphide, the preparation method is simple and easy to control, and the P/carrier has excellent catalytic performance and stability when being applied to the electrolysis of seawater for long-term electrolysis.

Description

Ni 12 P 5 Or Ni 2 Preparation method and application of P nano array
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to Ni 12 P 5 Or Ni 2 A preparation method and application of a P nano array.
Background
With the development of society, people rely on fossil energy more and more seriously, and cause environmental problems more and more seriously, at present, the people are dedicated to searching a new energy source which has high energy density and no pollution to the environment. The research of hydrogen energy by people finds that hydrogen has the characteristics of high energy density, no environmental pollution caused by combustion water and the like. The seawater electrolysis for hydrogen production has great development potential, but still has many problems, mainly limited by the price of noble metal catalyst, low yield and other disadvantages, and also limited by the complex environment of seawater, mainly the selective reaction at the anode and the corrosion problem of Cl-to the electrode surface. Based on the above problems, transition metal catalysts have been explored for the electrolysis of seawater to produce hydrogen.
The transition metal phosphide has excellent electrochemical performance and is widely concerned by researchers, and researches show that the phosphide is easy to prepare stable nano and micro structures which have remarkably strong stability and increased catalytic activity in electrolyzed water, so that the transition metal phosphide is an excellent electrode material. Phase studies have shown that nickel phosphide possesses a variety of compounds, such as: ni 3 P、Ni 2 P、NiP 2 、NiP、Ni 5 P 4 、Ni 7 P 3 、Ni 12 P 5 The bonding mode of nickel and phosphorus is special, and the bonding mode is generalThe synthesis method obtains phosphide NiP with different proportions X The preparation of single phosphide often requires complex synthesis formula and scheme, which is not favorable for the application of nickel phosphide in the direction of electrode material.
Disclosure of Invention
The invention provides a Ni 12 P 5 Or Ni 2 A preparation method and application of a P nano array at least solve the technical problems in the prior art.
The first aspect of the present invention provides Ni 12 P 5 Or Ni 2 A method of making a P-nanoarray, the method comprising:
pretreatment of a carrier: removing oxides and organic impurities on the surface of a carrier, wherein the carrier is used for providing a nickel source and providing a space for in-situ growth for the nano array;
preparation of Ni 12 P 5 Or Ni 2 P: covering phosphate on the pretreated carrier, heating to 250-350 ℃ in an inert atmosphere, preserving heat for 0.5-4h, washing and drying the obtained product to obtain Ni 12 P 5 Support or Ni 2 P/vector.
In one embodiment, the carrier is a nickel foam, a nickel copper foam, or a nickel iron foam.
In one embodiment, the carrier pretreatment comprises:
ultrasonically washing the carrier for 10-30min by using an acid solution;
then using an organic solvent to ultrasonically wash the carrier for 5-20 min;
and drying the washed carrier to obtain the pretreated carrier.
In one embodiment, the phosphate comprises one of an orthophosphate, a hypophosphite, or a phosphite.
In one embodiment, the mass ratio of the phosphate to the carrier is 3-6: 1.
In a second aspect, the present invention provides a NiSe 2 /TiN@Ni 12 P 5 Method for preparing supported catalyst, the Ni 12 P 5 The carrier is one of the aboveNi 12 P 5 Or Ni 2 The preparation method of the P nano array comprises the following steps:
mixing NiCl 2 -6H 2 O、SeO 2 And TiN are uniformly dissolved in deionized water to obtain a mixed solution;
adding the mixed solution into a polytetrafluoroethylene lining, heating to 130-160 ℃ at the speed of 1-10 ℃/min, preserving heat for 5h, filtering, washing and drying the obtained product to obtain NiSe 2 /TiN@Ni 12 P 5 A supported catalyst.
A third aspect of the present invention provides a NiSe 2 /TiN@Ni 2 Preparation of P/supported catalyst, Ni 2 P/carrier is Ni according to one of the above 12 P 5 Or Ni 2 The preparation method of the P nano array comprises the following steps:
mixing NiCl 2 -6H 2 O、SeO 2 And TiN are uniformly dissolved in deionized water to obtain a mixed solution;
adding the mixed solution into a polytetrafluoroethylene lining, heating to 130-160 ℃ at the speed of 1-10 ℃/min, preserving heat for 5h, filtering, washing and drying the obtained product to obtain NiSe 2 /TiN@Ni 2 P/carrier catalyst.
The fourth aspect of the present invention provides Ni 3 Se 2 /MoO 2 @Ni 12 P 5 Method for preparing supported catalyst, the Ni 12 P 5 The carrier is Ni 12 P 5 Or Ni 2 The preparation method of the P nano array comprises the following steps:
mixing ethylene glycol and choline chloride, and stirring at 50-100 ℃ to obtain a eutectic solvent;
adding NiCl into the eutectic solvent 2 -6H 2 O、(NH 4 ) 2 MoO 4 、C 6 H 8 O 7 And SeO 2 Stirring again to obtain a deposition solution;
the surface of the working electrode is simultaneously oxidized by an electrodeposition method under a three-electrode systemReduction reaction to obtain Ni 3 Se 2 /MoO 2 @Ni 12 P 5 A supported catalyst.
In one embodiment, the electrodeposition method comprises: with Ni 12 P 5 The carrier is a working electrode, the platinum column is a counter electrode, the silver wire is a reference electrode, and the deposition potential is as follows: -0.85V, deposition 10 Ccm -2. Then washing the surface of the catalyst electrode with deionized water, and finally drying.
The fifth aspect of the present invention provides Ni 12 P 5 Support or Ni 2 Application of P/carrier in electrolysis of seawater by adding Ni 12 P 5 Support or Ni 2 The P/carrier is used as an anode catalyst for oxygen evolution reaction of seawater electrolysis.
In the above scheme of the present invention, Ni is prepared by the method of the present invention 12 P 5 Support or Ni 2 The P/carrier can obtain single phosphide, the preparation method is simple and easy to control, and the P/carrier is applied to electrolysis of seawater for a long time and has excellent catalytic performance and stability.
Drawings
FIG. 1 shows Ni obtained in example 1 12 P 5 XRD pattern of/NF;
FIG. 2 shows Ni obtained in example 1 12 P 5 SEM and TEM images of/NF;
FIG. 3 shows Ni obtained in example 1 12 P 5 the/NF carries out LSV test under different systems;
FIG. 4 shows Ni obtained in example 1 12 P 5 A 200h long-term stability profile for NF;
FIG. 5 shows Ni obtained in example 1 12 P 5 Comparison of LSV performance of the material before and after 200 hours of NF electrolysis;
FIG. 6 is an XRD pattern after 200 hours of electrolysis for example 1;
FIG. 7 shows LSV tests carried out on different substances obtained in example 4;
FIG. 8 shows LSV tests performed on various materials prepared in example 5.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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 invention.
The invention provides a Ni 12 P 5 Or Ni 2 A method of making a P-nanoarray, the method comprising:
step S1, carrier pretreatment: removing oxides and organic impurities on the surface of a carrier, wherein the carrier is used for providing a nickel source and providing a space for in-situ growth for the nano array;
step S2, preparation of Ni 12 P 5 Or Ni 2 P: covering phosphate on the pretreated carrier, heating to 250-350 ℃ in an inert atmosphere, preserving heat for 0.5-4h, washing and drying the obtained product to obtain Ni 12 P 5 Support or Ni 2 P/vector.
In one embodiment, the carrier is Nickel Foam (NF), Nickel Copper Foam (NCF), or Nickel Iron Foam (NIF).
In one embodiment, the carrier pretreatment comprises:
ultrasonically washing the carrier for 10-30min by using an acid solution;
then using an organic solvent to ultrasonically wash the carrier for 5-20 min;
and drying the washed carrier to obtain the pretreated carrier.
In one embodiment, the phosphate comprises one of orthophosphate, hypophosphite, or phosphite.
In one embodiment, the mass ratio of the phosphate to the carrier is 3-6: 1.
The present invention will be described in detail with reference to specific examples.
Example 1
Ni 12 P 5 A method of preparing a nanoarray, the method comprising:
step S11, carrier pretreatment: removing oxides and organic impurities on the surface of a carrier, wherein the carrier is used for providing a nickel source and providing a space for in-situ growth for the nano array;
wherein the carrier is foam Nickel (NF), cutting the foam nickel into a size of 1cm multiplied by 2cm, respectively ultrasonically washing for 20min and 10min by using 1.0mol/L hydrochloric acid solution and absolute ethyl alcohol, removing oxides and organic impurities on the surface of the foam nickel, placing the washed foam nickel in a vacuum drying oven at 40 ℃, and drying for 2 h.
Step S12, preparation of Ni 12 P 5 Nano-array: putting 4 pretreated foamed nickel sheets into a porcelain boat, weighing 1g of anhydrous sodium hypophosphite to cover the foamed nickel sheets, putting the porcelain boat into a tube furnace, heating to 300 ℃ under the protection of nitrogen, and preserving heat for 2 hours; wherein the temperature rise interval is 20-300 ℃, the temperature rise rate is 5 ℃/min, and the nitrogen flow rate is as follows: 2L/min; repeatedly washing the obtained product with deionized water, placing the washed product in a vacuum drying oven at 40 ℃, and drying for 12h to obtain Ni 12 P 5 The nanoarray is denoted as Ni 12 P 5 /NF。Ni 12 P 5 The characterization and performance of NF:
(1) XRD characterization: FIG. 1 shows the diffraction pattern, Ni, obtained by XRD analysis 12 P 5 NF existing on diffraction pattern of/NF 12 P 5 Characteristic peak of (a);
(2) electron micrograph: scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) are adopted for Ni 12 P 5 The microstructure of/NF was characterized as shown in FIG. 2, where FIG. 2(a) is Ni 12 P 5 SEM image of/NF, it has nanometer array structure; FIG. 2(b) shows Ni 12 P 5 TEM image of/NF.
(3)Ni 12 P 5 The NF is used for carrying out catalytic performance test under different electrolyte systems: ni 12 P 5 the/NF catalyst was tested in a three-electrode system and in an alkaline solution with 1.0M KOH and 1.0M KOH plus 0.5M NaCl as electrolytes, as shown in FIG. 3, in 1.0M KOH plus 0.5M NaCl electrolyteThe tested performance is better than that of a test system with 1.0M KOH and the density is 100mA cm -2 Only 233mV overpotential is needed, and the performance can be compared with that of noble metal.
(4)Ni 12 P 5 Stability test of/NF: as shown in FIGS. 4 and 5, when the current density reached 100mA cm -2 The potential of the electrolyzed seawater is 91mV lower than that of the electrolyzed fresh water, and when the current density reaches 100mA cm in the electrolyzed seawater -2 Only 233mV overpotential is needed, and the material has excellent stability, and the final product Ni is tested in a 1.0M KOH and 0.5M NaCl system 12 P 5 Stability of/NF, it can be seen that at 100mA cm -2 After the electrolysis is continued for a long time of 200 hours, the potential is not increased but reduced by 22.9 mV. Analysis shows that as shown in FIG. 6, the XRD pattern of the catalyst after 200 hours of electrolysis shows that the surface of the catalyst is reformed to form Ni (OH) 2 。
Example 2
Ni 2 A method for preparing a P-nanoarray, the method comprising:
step S21, carrier pretreatment: removing oxides and organic impurities on the surface of a carrier, wherein the carrier is used for providing a nickel source and providing a space for in-situ growth for the nano array;
wherein the carrier is foam Nickel (NF), cutting the foam nickel into the size of 1cm multiplied by 2cm, respectively ultrasonically washing for 10min and 5min by using 1.0mol/L hydrochloric acid solution and propanol, removing oxides and organic impurities on the surface of the foam nickel, placing the washed foam nickel in a vacuum drying oven at 40 ℃, and drying for 2 h.
Step S22, preparation of Ni 2 P, nano array: putting 5 pretreated foamed nickel sheets into a porcelain boat, weighing 1g of anhydrous sodium hypophosphite to cover the foamed nickel sheets, putting the porcelain boat into a tube furnace, heating to 250 ℃ under the protection of nitrogen, and preserving heat for 2 hours; wherein the temperature rise interval is 20-250 ℃, the temperature rise rate is 2.5 ℃/min, and the nitrogen flow rate is as follows: 2L/min; repeatedly washing the obtained product with deionized water, placing the washed product in a vacuum drying oven at 40 ℃, and drying for 12h to obtain Ni 2 P nanoarrays are denoted Ni 2 P/NF。
Example 3
Ni 12 P 5 A method of preparing a nanoarray, the method comprising:
step S31, carrier pretreatment: removing oxides and organic impurities on the surface of a carrier, wherein the carrier is used for providing a nickel source and providing a space for in-situ growth for the nano array;
the carrier is foam Nickel Copper (NCF), the foam nickel copper is cut into a size of 1cm multiplied by 2cm, 1.0mol/L hydrochloric acid solution and absolute ethyl alcohol are respectively used for ultrasonic washing for 30min and 20min to remove oxides and organic impurities on the surface of the foam nickel copper, and the washed foam nickel copper is placed in a vacuum drying oven at the temperature of 40 ℃ and dried for 2 h.
Step S32, preparation of Ni 12 P 5 Nano-array: putting 4 pretreated foamed nickel copper sheets into a porcelain boat, weighing 1g of sodium orthophosphate to cover the foamed nickel copper sheets, putting the porcelain boat into a tubular furnace, heating to 350 ℃ under the protection of nitrogen and preserving heat for 0.5 h; wherein the temperature rise interval is 20-350 ℃, the temperature rise rate is 5 ℃/min, and the nitrogen flow rate is as follows: 2L/min; repeatedly washing the obtained product with deionized water, placing the washed product in a vacuum drying oven at 40 ℃, and drying for 12h to obtain Ni 12 P 5 The nanoarray is denoted as Ni 12 P 5 /NCF。
Example 4
NiSe 2 /TiN@Ni 12 P 5 Method for the production of/NF catalysts, in which Ni 12 P 5 the/NF preparation was the same as in example 1, and the process included:
step S41, 2.3mmol L -1 NiCl 2 -6H 2 O、10mmol L -1 SeO 2 And 0.16mmol L -1 Uniformly dissolving TiN in 100mL of deionized water to obtain a mixed solution;
step S42, adding the mixed solution prepared in the step S41 into a polytetrafluoroethylene lining, heating to 140 ℃ at the heating rate of 5 ℃/min, and preserving heat for 5 hours to obtain NiSe 2 /TiN@Ni 12 P 5 a/NF catalyst.
And (3) performance testing: NiSe 2 /TiN@Ni 12 P 5 /NF catalyst, Ni 12 P 5 The LSV curve of the/NF catalyst and NF applied to the UOR system for urea assisted oxidation is shown in FIG. 7, wherein Ni 12 P 5 /NF catalyst at 100mA cm -2 Only 1.447V; NiSe 2 /TiN@Ni 12 P 5 /NF catalyst at 500mA cm -2 Is 1.962V.
Example 5
Ni 3 Se 2 /MoO 2 @Ni 12 P 5 Method for preparing/NF catalyst, wherein Ni 12 P 5 The preparation method of/NF is the same as that of example 1, and comprises the following steps:
step S51, mixing ethylene glycol and choline chloride according to the mass ratio of 2:1, and stirring at 75 ℃ to obtain a eutectic solvent;
step S52, adding 0.25mol/L NiCl into the eutectic solvent 2 -6H 2 O、0.05mol/L(NH 4 ) 2 MoO 4 、0.2mol/L C 6 H 8 O 7 And 20mmol/L SeO 2 Stirring again to obtain a deposition solution;
step S53, carrying out oxidation-reduction reaction on the surface of the working electrode under a three-electrode system by an electrodeposition method to obtain Ni 3 Se 2 /MoO 2 @Ni 12 P 5 a/NF catalyst. The method specifically comprises the following steps: with Ni 12 P 5 the/NF is a working electrode, the platinum column is a counter electrode and the silver wire is a reference electrode, and the deposition potential is as follows: -0.85V, deposition amount 10 Ccm -2. Washing the surface of the catalyst electrode with deionized water at 55 ℃, and finally drying in vacuum to obtain Ni 3 Se 2 /MoO 2 @Ni 12 P 5 a/NF catalyst.
And (3) performance testing: ni 3 Se 2 /MoO 2 @Ni 12 P 5 /NF catalyst, Ni 12 P 5 The LSV curve of the/NF catalyst and the NF applied to the UOR system of the urea auxiliary oxidation is shown in the figure 87, and when the urea oxidation reaches the industrial standard, the current density is 500mA cm -2 Ni (m) is 3 Se 2 /MoO 2 @Ni 12 P 5 the/NF catalyst only requires 1.797V.
The basic principles of the present application have been described above with reference to specific embodiments, but it should be noted that advantages, effects, etc. mentioned in the present application are only examples and are not limiting, and the advantages, effects, etc. must not be considered to be possessed by various embodiments of the present application. Furthermore, the foregoing disclosure of specific details is for the purpose of illustration and description and is not intended to be limiting, since the foregoing disclosure is not intended to be exhaustive or to limit the disclosure to the precise details disclosed.
The words such as "including," "comprising," "having," and the like, referred to in this application are open-ended words that mean "including, but not limited to," and are used interchangeably herein. The words "or" and "as used herein mean, and are used interchangeably with, the word" and/or, "unless the context clearly dictates otherwise. The word "such as" is used herein to mean, and is used interchangeably with, the phrase "such as but not limited to".
It is further noted that in the method of the present application, the steps may be decomposed and/or recombined, and these decomposition and/or recombination should be regarded as an equivalent solution of the present application.
The previous description of the disclosed aspects is provided to enable any person skilled in the art to make or use the present application. Various modifications to these aspects will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other aspects without departing from the scope of the application. Thus, the present application is not intended to be limited to the aspects shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
The foregoing description has been presented for purposes of illustration and description. Furthermore, the description is not intended to limit embodiments of the application to the form disclosed herein. While a number of example aspects and embodiments have been discussed above, those of skill in the art will recognize certain variations, modifications, alterations, additions and sub-combinations thereof.

Claims (10)

1. Ni 12 P 5 Or Ni 2 The preparation method of the P nano array is characterized by comprising the following steps:
pretreatment of a carrier: removing oxides and organic impurities on the surface of a carrier, wherein the carrier is used for providing a nickel source and providing a space for in-situ growth for the nano array;
preparation of Ni 12 P 5 Or Ni 2 P: covering phosphate on the pretreated carrier, heating to 250-350 ℃ in an inert atmosphere, preserving heat for 0.5-4h, washing and drying the obtained product to obtain Ni 12 P 5 Support or Ni 2 P/vector.
2. The method of claim 1, wherein the carrier is foamed nickel, a foamed nickel-copper alloy, or a foamed nickel-iron alloy.
3. The production method according to claim 1 or 2, wherein the carrier pretreatment comprises:
ultrasonically washing the carrier for 10-30min by using an acid solution;
then using an organic solvent to ultrasonically wash the carrier for 5-20 min;
and drying the washed carrier to obtain the pretreated carrier.
4. The method of claim 1, wherein the phosphate comprises one of orthophosphate, hypophosphite, or phosphite.
5. The method according to claim 1, wherein the mass ratio of the phosphate to the carrier is 3-6: 1.
6. NiSe 2 /TiN@Ni 12 P 5 The method for preparing the supported catalyst is characterized in that the Ni 12 P 5 The carrier is prepared by the method according to any one of claims 1 to 5, and the preparation method comprises the following steps:
mixing NiCl 2 -6H 2 O、SeO 2 And TiN are uniformly dissolved in deionized water to obtain a mixed solution;
adding the mixed solution into a polytetrafluoroethylene lining, heating to 130-160 ℃ at the speed of 1-10 ℃/min, preserving heat for 5h, filtering, washing and drying the obtained product to obtain NiSe 2 /TiN@Ni 12 P 5 A supported catalyst.
7. NiSe 2 /TiN@Ni 2 The preparation method of the P/carrier catalyst is characterized in that the Ni is 2 The P/carrier is prepared by the method according to any one of claims 1 to 5, and the preparation method comprises the following steps:
mixing NiCl 2 -6H 2 O、SeO 2 And TiN are uniformly dissolved in deionized water to obtain a mixed solution;
adding the mixed solution into a polytetrafluoroethylene lining, heating to 130-160 ℃ at the speed of 1-10 ℃/min, preserving heat for 5h, filtering, washing and drying the obtained product to obtain NiSe 2 /TiN@Ni 2 P/carrier catalyst.
8. Ni 3 Se 2 /MoO 2 @Ni 12 P 5 A method for preparing a supported catalyst, characterized in that Ni is 12 P 5 The carrier is prepared by the method according to any one of claims 1 to 5, and the preparation method comprises the following steps:
mixing ethylene glycol and choline chloride, and stirring at 50-100 ℃ to obtain a eutectic solvent;
adding NiCl into the eutectic solvent 2 -6H 2 O、(NH 4 ) 2 MoO 4 、C 6 H 8 O 7 And SeO 2 Stirring again to obtain a deposition solution;
performing oxidation-reduction reaction on the surface of the working electrode simultaneously under a three-electrode system by an electrodeposition method to obtain Ni 3 Se 2 /MoO 2 @Ni 12 P 5 A supported catalyst.
9. The production method according to claim 8, wherein the electrodeposition method comprises: with Ni 12 P 5 The carrier is a working electrode, the platinum column is a counter electrode, the silver wire is a reference electrode, and the deposition potential is as follows: -0.85V, deposition 10 Ccm -2 The catalyst electrode surface was then rinsed with deionized water and finally dried.
10. Ni prepared according to the method of any one of claims 1-5 12 P 5 Support or Ni 2 The application of the P/carrier in the electrolysis of seawater is characterized in that: mixing Ni 12 P 5 Support or Ni 2 The P/carrier is used as an anode catalyst for oxygen evolution reaction of seawater electrolysis.
CN202210498874.9A 2022-05-09 2022-05-09 Ni (nickel) 12 P 5 Or Ni 2 Preparation method and application of P nano array Active CN115044933B (en)

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