CN114808012A - Phosphide/binary metal nitride nano porous heterojunction electrocatalyst and preparation method and application thereof - Google Patents
Phosphide/binary metal nitride nano porous heterojunction electrocatalyst and preparation method and application thereof Download PDFInfo
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- 150000004767 nitrides Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000758 substrate Substances 0.000 claims abstract description 43
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- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 6
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- 238000011144 upstream manufacturing Methods 0.000 claims description 4
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 13
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- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract description 5
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- 230000007774 longterm Effects 0.000 abstract 1
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0602—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with two or more other elements chosen from metals, silicon or boron
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract
The invention provides a phosphide/binary metal nitride nano porous heterojunction electrocatalyst, a preparation method and application thereof, wherein an excellent oxygen evolution catalyst, namely nickel-iron double hydroxide, is used as a carrier, and a powerful three-function hydrogen evolution, oxygen evolution and urea oxidation electrocatalyst is prepared by skillfully constructing a composite heterojunction; the preparation method comprises the following steps: (1) carrying out thermal nitridation treatment on the nickel-iron layered double-metal hydroxide conductive substrate which grows in a hydrothermal mode to obtain a NiFeN/foam conductive substrate composite material; (2) soaking the NiFeN/foam conductive substrate composite material in a modification precursor cobalt ion solution, taking out and drying; (3) and (3) carrying out high-temperature phosphating treatment on the obtained composite material. The nano-porous heterojunction electrocatalyst prepared by the invention has three functions of efficient hydrogen evolution, oxygen evolution and organic micromolecule urea oxidation, can keep long-term stability under high current density, and achieves the basic conditions of industrial hydrogen production.
Description
Technical Field
The invention belongs to the technical field of electrocatalytic materials, and particularly relates to a phosphide/binary metal nitride nano porous heterojunction electrocatalyst, and a preparation method and application thereof.
Background
The excessive development and utilization of fossil fuels such as petroleum, natural gas, coal and the like not only causes the situation of global non-renewable energy shortage but also causes irreversible influence on the natural environment. In response to the energy crisis, people are urgently required to look at renewable clean energy sources capable of replacing the traditional fossil fuels. For this reason, renewable energy sources in the form of wind energy, solar energy, tidal energy, geothermal energy, and the like are ideal choices, but the great influence of the natural environment on the renewable energy sources, uncontrollable nature, and intermittency become a great development problem. Therefore, the electric energy which can be generated by using renewable energy exists in a chemical bonding mode, and the renewable energy, namely hydrogen energy which is green, pollution-free, recyclable and controllable, is considered as the currently accepted low-carbon and pollution-free clean energy.
The hydrogen has the advantages of good thermal conductivity (10 times higher than that of most gases), high calorific value (142.351kJ/kg), only water as a product after combustion, recyclability, greenhouse effect reduction, no toxicity, easy transportation and the like. The method is irreplaceable in various industries such as novel high-energy fuel, metal smelting, petroleum refining, ammonia industry and the like. Various hydrogen production approaches (methane steam reforming, water gas method, hydrogen production by water electrolysis, and the like) have been developed so far, but various hydrogen production approaches are still to be perfected in consideration of the problems of industrial benefit, cleanness, environmental protection, energy resource utilization rate, and the like. Compared with the methane steam reforming or water gas method, the water electrolysis hydrogen production technology, such as an alkaline electrolytic cell, a chlor-alkali electrolytic cell, a proton exchange membrane electrolytic cell, a solid oxide water electrolysis hydrogen production technology, and the like, has strong renewability,The hydrogen production has high purity, cleanness, environmental protection and the like, is expected to become the mainstream mode of hydrogen production in the future, and the alkaline electrolyzed water has greater commercial potential and wider development space. It is foreseeable that the era of hydrogen energy being able to carry the double carbon goal is moving forward to us silently. However, the major bottlenecks that currently limit the large-scale application of the technology are the problems of poor activity and high overpotential of the catalyst, large power consumption, high hydrogen production cost and the like. Noble metal material (Pt, IrO) 2 Ru, etc.) are considered to be the most effective hydrogen-evolution, oxygen-evolution electrocatalysts, but the cost and scarcity of noble metals have hindered their large-scale application. Therefore, in order to reduce the hydrogen production cost, the development of a high-efficiency and stable non-noble metal catalyst to replace noble metal to develop the hydrogen production industry by alkaline electrolysis of water is urgently needed.
In recent years, in order to develop the technology of hydrogen production by electrolyzing water, a plurality of non-noble metal hydrogen evolution catalysts with excellent catalytic activity, such as layered materials (MoS), have been developed 2 、WS 2 Etc.), transition metal phosphides (CoP, FeP, CoPS, etc.), pyrite-type chalcogenides (CoS) 2 、CoSe 2 Etc.) and the like. However, most non-noble metal catalysts only maintain excellent hydrogen evolution activity in an acidic environment, and the hydrogen evolution activity in an alkaline environment needs to be further improved. In fact, compared with the acid environment, the industrial alkaline electrolytic cell hydrogen production technology is more mature in development, lower in price and wider in application prospect in China. Therefore, researchers expend a great deal of energy to explore efficient non-noble metal oxygen evolution catalysts which can be used in alkaline environments, mainly including transition metal (hydroxyl) oxides, phosphides, sulfides, selenides, metaphosphoric acid, bimetallic hydroxides and the like, but most of the non-noble metal catalysts have poor hydrogen evolution activity, and the researches are few in relation to the research of high-current stability and difficult to apply to industrial development. Therefore, it is necessary to develop a non-noble metal catalyst with high hydrogen evolution efficiency or excellent hydrogen evolution and oxygen evolution activities in an alkaline environment, and to realize high-current, high-efficiency and stable hydrogen production in the alkaline environment, which is a practical requirement of the alkaline water electrolysis hydrogen production technology for industrial application.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and defects mentioned in the background technology and provide a phosphide/binary metal nitride nano porous heterojunction electrocatalyst and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of phosphide/binary metal nitride nano-porous heterojunction electrocatalyst comprises the following steps:
(1) carrying out thermal nitridation treatment on the foamed conductive substrate on which the nickel-iron layered double hydroxide grows to obtain a NiFeN/foamed conductive substrate composite material;
(2) dissolving cobalt salt in dimethylformamide to obtain a modified precursor solution; soaking the NiFeN/foam conductive substrate composite material in the modification precursor solution, and then taking out and drying;
(3) and (3) carrying out high-temperature phosphating treatment on the composite material obtained by the treatment in the step (2) to obtain the phosphide/binary metal nitride nano porous heterojunction electrocatalyst.
Preferably, in the step (1), during the thermal nitridation, ammonia gas is used as a reaction gas, argon gas is used as a protective gas and a carrier gas, the temperature is raised to 350-. Different thermal nitriding treatments can obviously change the shape of the nickel-iron layered hydroxide, can adjust the inherent activity of the nickel-iron layered hydroxide, and enhance the hydrogen evolution performance of the nickel-iron layered hydroxide, if the temperature is low, incomplete nitriding is easy to cause, the conductivity of the nickel-iron layered hydroxide is reduced, and if the temperature is too high, the nano layered structure is changed, the layered shape is sintered and shrunk into particles, so that the specific surface area and the number of active sites in the water electrolysis process are not increased.
Preferably, in the step (1), the temperature rise rate is 5-10 ℃/min during the thermal nitridation treatment; the flow rate of the ammonia gas is 50-100sccm, and the flow rate of the argon gas is 10-50 sccm.
Preferably, in the step (2), the cobalt salt is one or more of cobalt nitrate hexahydrate and cobalt chloride; the concentration of cobalt salt in the modified precursor solution is 0.15-1 mol/L.
Preferably, in the step (2), the soaking time is 2-10 s. After soaking, the composite material is taken out by using tweezers and is placed in a fume hood for airing.
Preferably, the step (3) specifically comprises the following steps: placing a quartz boat containing phosphorus powder in the center of an upstream temperature zone of the gas of the dual-temperature-zone tube furnace, and setting the temperature to be 350-450 ℃; and (3) placing the composite material obtained by the treatment in the step (2) in the center of a temperature zone at the downstream of the double-temperature-zone tubular furnace, heating to 390 plus 500 ℃, and keeping the temperature for 0.5-2h to finally obtain the phosphide/binary metal nitride nano porous heterojunction electrocatalyst.
The high-temperature phosphating treatment can adjust the center of a d-band of an electrocatalyst to shrink the d-band, is beneficial to reducing the adsorption energy of electrolyzed water and reducing the potential of water splitting, and can lead a foam substrate to be phosphated if the phosphating temperature is not too high, thereby being not surface modification.
Preferably, in step (1), the foamed conductive substrate grown with the nickel-iron layered double hydroxide is prepared by the following method:
(a) cutting the foam conductive substrate, and carrying out ultrasonic cleaning by using hydrochloric acid, absolute ethyl alcohol and high-purity water in sequence to remove oxides on the surface to obtain a clean foam conductive substrate; wherein the hydrochloric acid can be 3M hydrochloric acid, anhydrous alcohol, and high purity water, and the ultrasonic cleaning time can be 10 min.
(b) Dissolving nickel salt, urea, ferric salt and ammonium fluoride in deionized water to obtain a hydrothermal precursor aqueous solution; placing a hydrothermal precursor aqueous solution into a lining of a hydrothermal reaction kettle, adding the foam conductive substrate obtained by the treatment in the step (a), screwing down the reaction kettle, transferring the reaction kettle into a vacuum drying box, standing for 30-60min, and heating at constant temperature of 120-150 ℃ for 6-8 h; and then cooling to room temperature, taking out and placing in high-purity water for soaking, taking out and airing to obtain the foam conductive substrate with the nickel-iron layered double hydroxide.
Preferably, in the step (a), the foamed conductive substrate is one of foamed nickel, foamed cobalt and foamed nickel cobalt;
in the step (b), the nickel salt is one or more of nickel nitrate hexahydrate and nickel chloride, and the iron salt is one or more of ferric nitrate nonahydrate and ferric chloride; the molar ratio of the nickel salt to the iron salt to the urea to the ammonium fluoride is 0.5: 0.16: 5: 2.5; the mass-volume ratio of the total mass of the nickel salt, the urea, the ferric salt and the ammonium fluoride to the volume of the deionized water is 0.604 g: 20 mL.
As a general inventive concept, the present invention provides a phosphide/binary metal nitride nanoporous heterojunction electrocatalyst, which is prepared by the above preparation method to obtain an electrocatalytic material, the surface morphology of which has a micro-nano particle structure grown on a nanosheet array, and the phosphide/binary metal nitride nanoporous heterojunction electrocatalyst comprises cobalt phosphide, nickel phosphide and nickel nitride crystals. The phosphide/binary metal nitride nano porous heterojunction electrocatalyst is a high-efficiency material for electrolyzing water and separating hydrogen, and is applied to hydrogen energy and organic micromolecule oxidized urea electrolysis hydrogen production.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the porous heterojunction of the phosphide/binary metal nitride nano porous heterojunction is constructed, the advantages of nitride and phosphide are integrated, the interface synergistic enhancement effect is formed, the conductivity and stability of the catalyst are improved through thermal nitridation treatment, and the d-band center is regulated through the phosphating treatment, so that the nano porous structure of the catalyst is favorable for providing a higher specific surface area, the active site of an electrocatalytic material is further exposed, the rapid charge transfer and the substance transfer are facilitated, and the catalytic performance of the material is effectively improved.
2. According to the invention, by means of a hydrothermal method and a chemical vapor deposition method, transition metal iron, cobalt and nickel and nonmetal nitrogen and phosphorus elements are combined to form a transition metal nitrogen and phosphorus compound heterojunction, and the electrocatalysis performance is further improved by the synergistic catalysis effect of various transition metals. Further, by means of the high conductivity and the high specific surface area of the nano array and the high catalytic activity of the nano particles, the water decomposition voltage and the energy consumption of a full-water-decomposing device under a large current are reduced, and stable hydrogen production under a low voltage and a large current is realized.
3. The method has the advantages of low raw material cost, low energy consumption, stable and reliable process, simple operation and easy mastering, and realizes the double effects of high-efficiency energy conversion (hydrogen production) and urea pollution removal.
4. The invention develops a multifunctional electrocatalyst with excellent large-current hydrogen evolution, oxygen evolution and organic micromolecule urea oxidation performance for the first time, and the electrocatalyst can be used for hydrogen production by water electrolysis, the research field of new energy and urea fuel cells.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a scanning electron micrograph of a foamed nickel substrate grown with nickel-iron layered double hydroxide (NiFe LDH);
FIG. 2 is a scanning electron micrograph of a CoP/NiFeN nanoporous heterojunction electrocatalyst;
FIG. 3 is an X-ray diffraction pattern of a CoP/NiFeN nanoporous heterojunction electrocatalyst;
FIG. 4 is a graph of current-potential polarization of hydrogen evolution reaction of CoP/NiFeN nanoporous heterojunction electrocatalyst in 1M KOH alkaline environment initially and after 1000 cycles;
FIG. 5 is a stability test curve of hydrogen evolution reaction of CoP/NiFeN nanoporous heterojunction electrocatalyst in 1M KOH electrolyte;
FIG. 6 is a graph of oxygen evolution reaction current-potential polarization for CoP/NiFeN nanoporous heterojunction electrocatalysts in 1M KOH electrolyte initially and after 1000 cycles;
FIG. 7 is a stability test curve of oxygen evolution reaction of CoP/NiFeN nanoporous heterojunction electrocatalyst in 1M KOH electrolyte;
FIG. 8 is a graph of urea oxidation current-potential polarization for CoP/NiFeN nanoporous heterojunction electrocatalyst in 1M KOH +0.5M urea electrolyte initially and after 1000 cycles;
FIG. 9 is a graph of a stability test of the oxidation of urea in 1M KOH +0.5M urea electrolyte for a CoP/NiFeN nanoporous heterojunction electrocatalyst;
FIG. 10 is a graph of the current-potential polarization of the full water splitting performance of CoP/NiFeN nanoporous heterojunction electrocatalyst in 1M KOH electrolyte initially and after 250 cycles.
FIG. 11 is a graph of a CoP/NiFeN nanoporous heterojunction electrocatalyst test curve for full water splitting performance stability in 1M KOH electrolyte.
FIG. 12 is a graph of the reaction current-potential polarization performance of CoP/NiFeN nanoporous heterojunction electrocatalyst for total urea hydrolysis in 1M KOH +0.5M urea electrolyte initially and after 250 cycles.
FIG. 13 is a graph of the stability of the CoP/NiFeN nanoporous heterojunction electrocatalyst performance in the all-urea hydrolysis in 1M KOH +0.5M urea electrolyte.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a preparation method of a phosphide/binary metal nitride nano-porous heterojunction electrocatalyst comprises the following steps:
(1) the commercial foam nickel substrate purchased is cut into a shape with the length of 4.3cm and the width of 2.2cm, the cut foam nickel substrate is subjected to ultrasonic cleaning, and hydrochloric acid, ethanol and deionized water are sequentially subjected to ultrasonic cleaning for 10 min.
(2) 0.144g of Ni (NO) 3 ) 2 ·6H 2 O, 0.3g urea, 0.067g Fe (NO) 3 ) 3 ·9H 2 O、0.093g NH 4 F is fully dissolved in 20ml of deionized water to obtain a hydrothermal precursor reaction solution; filling the hydrothermal precursor reaction solution into a hydrothermal reaction kettle lining, and soaking the cleaned foam nickel substrate into the hydrothermal precursor reaction solution; and (3) screwing the reaction kettle, placing the reaction kettle into a vacuum drying oven, standing for 30min, heating at constant temperature of 120 ℃ for 6h, cooling the vacuum drying oven to room temperature after the reaction is finished, taking out a sample, placing the sample in high-purity water for soaking for half an hour to remove redundant reaction solution, and then placing the sample in a fume hood for airing to obtain the foamed nickel substrate with the layered nickel-iron bimetal hydroxide.
(3) And (3) thermal nitridation treatment: placing the foamed nickel substrate with the nickel-iron layered double hydroxide in the center of a temperature zone of a tubular furnace, taking ammonia gas with the flow rate of 100sccm as reaction gas and argon gas with the flow rate of 10sccm as protective gas and carrier gas, setting the temperature at 400 ℃, heating at the rate of 5 ℃/min, heating to 400 ℃, keeping the temperature for 2 hours, and cooling to room temperature after the reaction is finished to obtain the NiFeN/foamed nickel substrate composite material.
(4) Co ion modification: 0.755Co (NO) 3 ) 2 ·6H 2 And fully dissolving O in 5ml of dimethylformamide organic solvent to obtain a modification precursor solution, soaking the NiFeN/foamed nickel substrate composite material obtained by the operation in the modification precursor solution for 2-3s, taking out and placing in a fume hood for natural airing to obtain the cobalt ion modified NiFeN/foamed nickel substrate composite material.
(5) High-temperature phosphating treatment: placing a quartz boat containing 50mg of phosphorus powder in the center of an upstream temperature zone of gas of a double-temperature-zone tubular furnace, and setting the temperature to be 390 ℃; and (3) placing the NiFeN/foamed nickel substrate composite material modified by the cobalt ions obtained by the treatment in the step (4) in the center of a downstream temperature zone, setting the temperature at 400 ℃, raising the temperature at a rate of 10 ℃/min, keeping the temperature at the constant temperature for 1h after raising the temperature to 400 ℃, and cooling the temperature of the tube furnace to room temperature to obtain the phosphide/binary metal nitride nano porous heterojunction electrocatalyst (namely the CoP/NiFeN nano porous heterojunction electrocatalyst).
Wherein, a scanning electron microscope image of the foamed nickel substrate grown with the nickel-iron layered double hydroxide (NiFe LDH) prepared in the step (2) is shown in figure 1, so that a large number of nanosheet arrays are uniformly distributed on the foamed nickel framework, the subsequent treatment steps are facilitated, the contact area between the nanosheet arrays and the electrolyte is increased, more active sites are exposed, and the potential barrier of the whole reaction process is reduced; a scanning electron microscope image of the CoP/NiFeN nano porous heterojunction electrocatalyst is shown in fig. 2, and by looking at the scanning electron microscope image, compared with a hydrothermal substrate nickel-iron layered double hydroxide, the nano sheet surface is rougher, more particles are attached to the surface, and the cobalt phosphide particles are successfully attached from the side surface; the X-ray diffraction spectrogram is shown in figure 3, and the synthesized CoP/NiFeN nano heterojunction electrocatalyst is basically composed of cobalt phosphide, nickel phosphide and cobaltous nitride, which shows that the CoP/NiFeN nano heterojunction is successfully synthesized through thermal nitrogen and high-temperature phosphating.
Example 2:
a second preparation method of the phosphide/binary metal nitride nano-porous heterojunction electrocatalyst comprises the following steps:
(1) the commercial foam nickel substrate purchased was cut into a shape of 4.3cm in length by 2.2cm in width, and the cut foam nickel substrate was subjected to ultrasonic cleaning for 10min in sequence in 3M hydrochloric acid, ethanol, deionized water.
(2) 0.144g of Ni (NO) 3 ) 2 ·6H 2 O, 0.3g urea, 0.067g Fe (NO) 3 ) 3 ·9H 2 O、0.093g NH 4 F is fully dissolved in 20ml of deionized water to obtain a hydrothermal precursor reaction solution; filling the hydrothermal precursor reaction solution into a hydrothermal reaction kettle lining, and soaking the cleaned foam nickel substrate into the hydrothermal precursor reaction solution; screwing down the reaction kettle, placing into a vacuum drying oven, standing for 60min, and standing at 120 deg.CAnd (3) heating at constant temperature for 6h, after the reaction is finished, cooling the sample in a vacuum drying oven to room temperature, taking out the sample, placing the sample in high-purity water, soaking the sample for half an hour to remove redundant reaction solution, and then placing the sample in a fume hood for airing to obtain the foamed nickel substrate on which the layered double metal hydroxide of the nickel-iron is grown.
(3) And (3) thermal nitridation treatment: placing the foamed nickel substrate with the nickel-iron layered double hydroxide in the center of a temperature zone of a tubular furnace, taking ammonia gas with the flow rate of 100sccm as reaction gas and argon gas with the flow rate of 10sccm as protective gas and carrier gas, setting the temperature to 380 ℃, heating at the rate of 5 ℃/min, heating to 380 ℃, keeping the temperature for 2 hours, and cooling to room temperature after the reaction is finished to obtain the NiFeN/foamed nickel substrate composite material.
(4) Modifying with Co ion, changing the concentration of modifying solution, and adding 1g (or 0.5g) Co (NO) 3 ) 2 ·6H 2 And fully dissolving O in 5ml of dimethylformamide organic solvent to obtain a modification precursor solution, soaking the NiFeN/foam nickel substrate composite material obtained by the operation in the modification precursor solution for 2-3s, taking out, placing in a fume hood, and naturally airing to obtain the cobalt ion modified NiFeN/foam nickel substrate composite material.
(5) High-temperature phosphating treatment: placing a quartz boat containing 50mg of phosphorus powder in the center of an upstream temperature zone of gas of a double-temperature-zone tube furnace, and setting the temperature to be 400 ℃; and (3) placing the NiFeN/foamed nickel substrate composite material modified by the cobalt ions obtained by the treatment in the step (4) in the center of a downstream temperature zone, setting the temperature at 390 ℃, heating the temperature at a heating rate of 10 ℃/min to 390 ℃, keeping the temperature for 0.5h, and cooling the temperature of the tubular furnace to room temperature to obtain the phosphide/binary metal nitride nano porous heterojunction electrocatalyst (namely the CoP/NiFeN nano porous heterojunction electrocatalyst).
Example 3:
the catalytic performance of the CoP/NiFeN nano-porous heterojunction obtained in example 1 is subjected to an electrocatalytic performance test. The device used for the electrocatalysis performance test is an electrochemical workstation of a known American brand GAMRYReference 3000, and a standard three-electrode system is adopted for the test. Wherein the three-electrode system: CoP/NiFeN nano-porous heterojunction electrocatalyst is used as a working electrode, Hg/HgO electrode imported by Gamry company is used as a reference electrode, high-purity graphite paper (more than 99 percent) is used as a counter electrode, performance tests of electrolytic water alkaline hydrogen evolution and electrolytic water alkaline oxygen evolution are respectively carried out in 1M KOH electrolyte, and electrochemical test curves are shown in figures 4, 5, 6 and 7.
Wherein, fig. 4 is a current-potential polarization curve diagram of hydrogen evolution reaction of the CoP/NiFeN nano-porous heterojunction electrocatalyst under 1M KOH alkaline environment at the beginning and after 1000 cycles, it can be seen that after 1000 cycles, the catalytic performance remains stable, and only 100mV of overpotential is needed to drive 176mA/cm 2 The current density of (2) has excellent alkaline hydrogen evolution performance; FIG. 5 is a stability test curve of CoP/NiFeN nano-porous heterojunction electrocatalyst hydrogen evolution reaction constant current potential timing, from which it can be assisted to prove that the catalyst is very stable and has excellent tolerance; FIG. 6 is the graph of the current-potential polarization curve of the oxygen evolution reaction of the CoP/NiFeN nanoporous heterojunction electrocatalyst during the first and 1000 cycles, and it can be seen that the synthesized nano-heterojunction can drive 500mA/cm by only 290mV of overpotential 2 The commercial current density of (2) has extremely excellent alkaline oxygen evolution performance; fig. 7 is a constant current potential stability test curve of the oxygen evolution reaction of the CoP/NiFeN nanoporous heterojunction electrocatalyst, and it can be seen that the prepared nano heterojunction still has lasting stability even under a high current density test, which indicates that the catalytic performance is excellent.
And (3) changing the electrolyte into 1M KOH +0.5M urea (urea) in the same operation flow, and carrying out the oxidation performance test of the organic micromolecule urea to obtain electrochemical test curve graphs 8 and 9. FIG. 8 is the urea oxidation current-potential polarization curve of CoP/NiFeN nanoporous heterojunction electrocatalyst at the beginning and after 1000 cycles, and it can be seen from the graph that the CoP/NiFeN nanoporous heterojunction prepared by the method only needs 1.384V potential to drive high current density 500mA/cm 2 The organic micromolecule urea has excellent oxidation performance; FIG. 9 is a constant current potentiometric stability test curve diagram of CoP/NiFeN nanoporous heterojunction electrocatalyst urea oxidation, which can directly show that the prepared CoP/NiFeN nanoporous heterojunction has lasting stabilityThe test of high current for a long time still keeps stable, and successfully solves the problem that the current density of the organic micromolecular urea is unstable.
Example 4:
the CoP/NiFeN nano-porous heterostructure prepared in the example 1 is respectively used as a positive electrode and a negative electrode to construct a standard two-electrode electrolytic cell, the full hydrolysis performance of the standard two-electrode electrolytic cell in an alkaline environment of 1M KOH is tested, and the linear sweep voltammetry curve and the constant current potentiometry curve are shown in FIGS. 10 and 11:
wherein FIG. 10 shows linear sweep voltammetry curves of a full-hydrolytic device, it can be seen from the graph that the curves of the prepared CoP/NiFeN nanoporous heterojunction are basically coincident after the initial and 250 cycles, and have good stability, and in particular, only voltages of 1.615V and 1.668V are required to stably drive 200mA/cm and 500mA/cm 2 The current density of (a) indicates that it has excellent perhydrolysis performance; FIG. 11 shows CoP/NiFeN nano-heterojunction at current densities of 200 and 500mA/cm 2 The oxidation potential of the catalyst does not change too much when the continuous test is close to 30h, and negligible activity weakening shows that the electrocatalyst has excellent full hydrolytic stability.
Example 5:
compared with the water electrolysis hydrogen production reaction with large energy consumption, the water electrolysis hydrogen production of urea is concerned by the unique advantages. (1) The theoretical total voltage (0.37V) of urea electrolysis is less than the theoretical voltage of water electrolysis, so that the energy consumption for producing hydrogen is lower, and the energy efficiency higher than that of the water electrolysis technology can be obtained; (2) urea is one of the major pollutants affecting soil and water. The urea catalytic oxidation reaction can decompose urea, which is beneficial to solving the problem of water pollution caused by waste water and realizing the double effects of clean energy conversion and changing waste into valuables; (3) in the process of hydrogen production, urea oxidation is adopted as an anode reaction, and O is not generated 2 Generation of O is avoided 2 And H 2 The prepared CoP/NiFeN nano-porous heterostructure is respectively used as a positive electrode and a negative electrode to construct a standard double-electrode electrolytic cell, and the standard double-electrode electrolytic cell is tested in an alkaline environment of 1M KOH +0.5M urea (urea)The full urea full-resolution performance, the linear sweep voltammogram and the constant current potential timing curve are shown in figures 12 and 13:
in FIG. 12, it can be seen that the linear sweep voltammetry curves of the fully hydrolyzed device are substantially coincident after the initial and 250 cycles of the prepared CoP/NiFeN, and have good stability, and in particular, only voltages of 1.508V and 1.577V are required to stably drive 200mA/cm and 500mA/cm 2 The current density of (a) indicates that it has excellent perhydrolysis performance; FIG. 13 shows a CoP/NiFeN nano-heterojunction with a current density of 200mA/cm 2 The continuous test is close to 30h, the urea oxidation potential is not changed too much, and the negligible activity decline shows that the electrocatalyst has excellent full urea hydrolysis stability.
Claims (10)
1. A preparation method of phosphide/binary metal nitride nano-porous heterojunction electrocatalyst is characterized by comprising the following steps:
(1) carrying out thermal nitridation treatment on the foam conductive substrate on which the nickel-iron layered double hydroxide grows to obtain a NiFeN/foam conductive substrate composite material;
(2) dissolving cobalt salt in dimethylformamide to obtain a modified precursor solution; soaking the NiFeN/foam conductive substrate composite material in the modification precursor solution, and then taking out and drying;
(3) and (3) carrying out high-temperature phosphating treatment on the composite material obtained by the treatment in the step (2) to obtain the phosphide/binary metal nitride nano porous heterojunction electrocatalyst.
2. The method as claimed in claim 1, wherein in the step (1), ammonia gas is used as the reaction gas, argon gas is used as the protective gas and the carrier gas, the temperature is raised to 350-480 ℃, the temperature is maintained for 1-3h, and the reaction is cooled to room temperature after the reaction is finished.
3. The method according to claim 1, wherein in the step (1), the temperature is raised at a rate of 5 to 10 ℃/min, the flow rate of ammonia gas is 50 to 100sccm, and the flow rate of argon gas is 10 to 50sccm during the thermal nitridation treatment.
4. The preparation method according to claim 1, wherein in the step (2), the cobalt salt is one or more of cobalt nitrate hexahydrate and cobalt chloride; the concentration of cobalt salt in the modified precursor solution is 0.15-1 mol/L.
5. The method according to claim 1, wherein the soaking time in the step (2) is 2 to 10 seconds.
6. The method according to claim 1, wherein the step (3) comprises the steps of: placing a quartz boat containing phosphorus powder in the center of an upstream temperature zone of the gas of the dual-temperature-zone tube furnace, and setting the temperature to be 350-450 ℃; and (3) placing the composite material obtained by the treatment in the step (2) in the center of a temperature zone at the downstream of the dual-temperature zone tubular furnace, heating to 390 ℃ and 500 ℃, and keeping the temperature for 0.5-2h to finally obtain the phosphide/binary metal nitride nano porous heterojunction electrocatalyst.
7. The method for preparing according to any one of claims 1 to 6, wherein in the step (1), the foamed conductive substrate grown with the layered double hydroxide of nickel-iron is prepared by:
(a) cutting the foam conductive substrate, and carrying out ultrasonic cleaning by using hydrochloric acid, absolute ethyl alcohol and high-purity water in sequence to obtain a clean foam conductive substrate;
(b) dissolving nickel salt, urea, ferric salt and ammonium fluoride in deionized water to obtain a hydrothermal precursor aqueous solution; placing a hydrothermal precursor aqueous solution into a lining of a hydrothermal reaction kettle, adding the foam conductive substrate obtained by the treatment in the step (a), screwing down the reaction kettle, transferring the reaction kettle into a vacuum drying box, standing for 30-60min, and heating at constant temperature of 120-150 ℃ for 6-8 h; and then cooling to room temperature, taking out and placing in high-purity water for soaking, taking out and airing to obtain the foam conductive substrate with the nickel-iron layered double hydroxide.
8. The method according to claim 7, wherein in the step (a), the foamed conductive substrate is one of foamed nickel, foamed cobalt and foamed nickel cobalt;
in the step (b), the nickel salt is one or more of nickel nitrate hexahydrate and nickel chloride, and the iron salt is one or more of ferric nitrate nonahydrate and ferric chloride; the molar ratio of the nickel salt to the iron salt to the urea to the ammonium fluoride is 0.5: 0.16: 5: 2.5; the mass-volume ratio of the total mass of the nickel salt, the urea, the ferric salt and the ammonium fluoride to the volume of the deionized water is 0.604 g: 20 mL.
9. A phosphide/binary metal nitride nanoporous heterojunction electrocatalyst prepared by the preparation method as claimed in any one of claims 1 to 8, comprising cobalt phosphide, nickel phosphide and nickel nitride crystals.
10. The application of the phosphide/binary metal nitride nano-porous heterojunction electrocatalyst prepared by the preparation method according to any one of claims 1 to 8 or the phosphide/binary metal nitride nano-porous heterojunction electrocatalyst according to claim 9 in hydrogen production by water electrolysis and hydrogen production by electrolysis of organic micromolecule oxidized urea.
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