CN114068952A - Integral transition metal nitride electrocatalyst with flower-like structure and preparation method and application thereof - Google Patents
Integral transition metal nitride electrocatalyst with flower-like structure and preparation method and application thereof Download PDFInfo
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- -1 transition metal nitride Chemical class 0.000 title claims abstract description 44
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 51
- 238000005121 nitriding Methods 0.000 claims abstract description 51
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- 150000003624 transition metals Chemical class 0.000 claims abstract description 14
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 9
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- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 4
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- 239000003607 modifier Substances 0.000 claims 2
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- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
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- 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
- Y02E60/50—Fuel cells
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses an integral transition metal nitride electrocatalyst with a flower-shaped structure and a preparation method and application thereof. The catalyst consists of transition metal nitride and a carrier material, wherein the transition metal nitride is loaded on the surface of the carrier material. The monolithic transition metal nitride electrocatalyst with a flower-like structure is obtained by adding a carrier material into an aqueous solution containing a transition metal precursor salt, a precipitator and a shape regulator, carrying out hydrothermal reaction at 80-180 ℃, and then carrying out nitriding heat treatment in a mixed atmosphere consisting of ammonia gas and inert gas at the temperature of 250-800 ℃. The preparation method of the invention has the advantages of low cost of raw materials, convenient preparation and easy mass production. The prepared catalyst has high intrinsic catalytic activity, abundant active sites and good conductivity, and can efficiently and stably catalyze the electrochemical oxidation reaction of hydrazine hydrate under an alkaline condition.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to an integral transition metal nitride electrocatalyst with a flower-shaped structure, and a preparation method and application thereof.
Background
Energy is the driving force of human economy and social development, along with rapid development of economy and society, the energy consumption intensity shows a high-speed growth situation, an energy consumption system mainly based on traditional fossil energy obviously cannot meet the long-term energy consumption requirement of human, and global problems of daily shortage of non-renewable energy resources, increasingly worsened ecological environment and the like are caused due to factors such as low energy efficiency and unreasonable energy consumption mode for long time use. Therefore, the development of a clean, low-carbon, safe, efficient and renewable energy conversion technology and the construction of an energy supply structure mainly based on new energy to optimize an energy supply system are particularly urgent to reduce the dependence on the traditional fossil energy. Among various renewable energy conversion technologies, fuel cells, which are a typical energy conversion device, have attracted attention due to their advantages, such as high energy conversion efficiency, wide fuel sources, and environmental friendliness.
The fuel cell has wide power specification and wide practical prospect due to the characteristics of various reaction fuels, various electrolyte types and the like, and can be used for large-scale power stations, portable electronic equipment and traffic power supplies. Among the alternative classes of fuel cells suitable for automotive or portable electronic devices, Direct Hydrazine Fuel Cells (DHFC) have a high energy density (5.42Wh · g)–1) The method has the advantages of high theoretical potential (1.56V), mild reaction conditions (40-80 ℃), no greenhouse gas effect and environmental negative effect of products, no need of noble metal catalysts and the like, and is concerned. Through decades of development, related researches on DHFC have been actively progressed, the design and modification of anode hydrazine oxidation electrocatalytic materials are particularly obvious, a large number of non-noble metal materials with excellent performance are reported and developed for DHFC anode catalysts, two effective modification strategies based on empirical trial type active component selection are summarized, one is to improve the intrinsic activity of the catalytic materials based on an electronic structure modulation strategy to improve the hydrazine electrooxidation activity of the catalytic materials, and the main means comprises element doping, alloying, compound formation or heterostructure interface construction and the like; the second method is to improve the apparent activity of the catalytic material by increasing the catalytic activity site number of the catalytic material based on a morphological structure regulation strategy, and the main means is the nano-structure engineering. One or more of the strategies can be combined for use to further improve the electrooxidation activity of the catalytic material to hydrazine molecules, and the method generates a plurality of representative DHFC anode electrocatalysts with excellent comprehensive performance. However, from the practical point of view, the performance of the hydrazine anode electrocatalyst reported at present is far from meeting the requirement of commercial application, and the development of an advanced, efficient and cheap hydrazine anode electrocatalyst is still the core topic for the development of the DHFC technology.
Transition Metal Nitrides (TMN) are a typical class of intermetallic compounds, covering a wide range of classes from metal-type nitrides, covalent-type nitrides to ionic-type nitrides, and generally possess unique electronic structures, excellent conductivity and chemical stability. Transition metal nitride materials have been extensively studied in the fields of electrolytic water, lithium ion batteries and supercapacitors due to their outstanding advantages, but in the field of DHFC research, studies on the application of transition metal nitrides have been rare, and thus, there is a potential application of transition metal nitrides as DHFC anode materials (j. mater. chem. a,2020,8, 632-. Therefore, based on the comprehensive consideration of the intrinsic activity of the catalytic material, the number of active sites, the conductivity and the like, the integral transition metal nitride electrocatalyst with a flower-shaped structure is designed and synthesized, is applied to the oxidation reaction of the DHFC anode hydrazine hydrate, is expected to contribute value to the development of the advanced design concept of the cheap metal catalyst and the controllable synthesis method, and is expected to promote the practical process of the direct hydrazine fuel cell technology.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide an integral transition metal nitride electrocatalyst with a flower-shaped structure and a preparation method and application thereof. The integral transition metal nitride electrocatalyst with a flower-like structure has high intrinsic activity, rich active sites and good conductivity for hydrazine electrochemical oxidation reaction, can efficiently and stably catalyze the hydrazine electrochemical oxidation reaction under an alkaline condition, and has comprehensive catalytic performance at the top level of the reported hydrazine oxidation electrocatalyst.
Another object of the present invention is to provide a method for preparing the monolithic transition metal nitride electrocatalyst with a flower-like structure as described above. The method has the advantages of easily available raw materials, simple operation and convenient mass production.
The purpose of the invention is realized by the following technical scheme:
a monolithic transition metal nitride electrocatalyst with flower-like structure, the electrocatalyst is composed of transition metal nitride and support material, the transition metal nitride is supported on the surface of the support material.
Preferably, the transition metal nitride is an active phase; the transition metal refers to one or a combination of more of Ni, Co, Fe, Cu, W, Mo or Mn.
Preferably, the transition metal nitride has a flower-like morphology structure, and the diameter of the flower-like morphology structure is 1-10 μm; the flower-shaped structure is composed of nanosheets, and the thickness of each nanosheet is 1-50 nm.
Preferably, the support material is selected from a metal foam, a metal mesh or a porous carbon material having an independent skeleton structure. More preferably Nickel Foam (NF). The porous carbon material with the independent skeleton structure is carbon cloth or carbon paper.
The preparation method of the monolithic transition metal nitride electrocatalyst with a flower-like structure comprises the following steps:
adding a carrier material into an aqueous solution containing a transition metal salt, a precipitator and a shape regulator, carrying out hydrothermal reaction at 80-180 ℃, growing a transition metal hydroxide or basic carbonate precursor with a flower-like structure on the surface of the carrier material, carrying out subsequent cleaning and drying, and carrying out nitriding heat treatment in a mixed atmosphere consisting of ammonia gas and inert gas at the temperature of 250-800 ℃ to obtain the integral transition metal nitride electrocatalyst with the flower-like structure.
Preferably, the transition metal salt refers to one or more of halide, nitrate, sulfate, sulfamate, acetate or other oxygen-containing or non-oxygen-containing acid salt of transition metal; the transition metal refers to one or a combination of more of Ni, Co, Fe, Cu, W, Mo or Mn.
Preferably, the concentration of the transition metal ions in the aqueous solution is 0.0001-0.3M;
preferably, the precipitant is at least one of ammonia water, hexamethylenetetramine, dimethyl oxalate, diethyl oxalate, urea and chlorohydrin; more preferably urea.
Preferably, the concentration of the precipitating agent in the aqueous solution is 0.0001-0.6M.
Preferably, the shape regulator is at least one of ammonium fluoride, sodium fluoride, calcium chloride and potassium chloride; more preferably ammonium fluoride.
Preferably, the concentration of the shape regulator in the aqueous solution is 0.0001-0.3M;
preferably, the hydrothermal reaction time is 4-48 hours.
Preferably, the nitriding heat treatment time is 0.5-6 hours, and the heating rate is 2-10 ℃/min; the nitriding heat treatment is carried out under the load flow of the mixed atmosphere of ammonia gas and inert gas; the carrier gas carrier flow rate is 30-200 ml/min; the inert gas is argon; the volume ratio of ammonia gas to inert gas in the mixed atmosphere is 0.05-1: 1.
the monolithic transition metal nitride electrocatalyst with a flower-like structure is used as an anode material for a hydrazine hydrate fuel cell.
The principle of the invention is as follows: the intrinsic activity, the number of active sites and the electrical conductivity of the electrocatalyst are the three major factors that influence the apparent catalytic activity. The design of the traditional electrocatalyst only considers one or two factors, but the invention aims to simultaneously optimize three major factors of the intrinsic activity, the number of active sites, the conductivity and the like of the electrocatalyst, and simultaneously provides a simple and easy preparation method to realize the aim and the purpose. Firstly, a transition metal hydroxide or basic carbonate precursor which contains a catalyst active component and has a flower-like structure and a high specific surface area is grown on the surface of a carrier material by a hydrothermal method, so that a material composition and a structural foundation are laid for synthesizing a high-performance catalyst; and then, converting the precursor of the transition metal hydroxide or the basic carbonate into the active phase of the transition metal nitride by regulating and controlling nitriding heat treatment conditions. The key to the electrochemical dissociation of hydrazine molecules on the catalyst surface is the adsorption process of hydrazine and the dehydrogenation process of hydrazine molecules. The transition metal nitride is used as an electrochemical oxidation active phase for catalyzing hydrazine, can provide active sites for adsorption and dehydrogenation reaction of hydrazine molecules, and compared with a hydrothermal precursor and a substrate NF, the metal nitride has the advantages of obviously improved conductivity, obviously increased electrochemical specific surface area and obviously improved electrocatalytic activity, and reflects improvement of nitridation heat treatment on intrinsic activity of the catalyst; the hydrothermally synthesized transition metal hydroxide or basic carbonate precursor is a flower-shaped structure with a high specific surface area, the retention of the flower-shaped structure in the nitriding heat treatment process reflects the high stability of the catalyst framework structure, and the supply of rich active sites in the electrocatalytic reaction process is ensured. In addition, the carrier material with porous conducting network structure is selected, so that the use of a binder can be avoided, and the mass transfer process can be improved while the supply of high-activity sites is ensured. In conclusion, the hydrazine oxidation catalyst provided by the invention has high intrinsic activity, abundant active sites and good conductivity.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) compared with the traditional preparation method of the electrocatalyst, the invention provides a simple and feasible preparation method, and realizes the simultaneous optimization of three major factors of the intrinsic activity, the number of active sites, the conductivity and the like of the electrocatalyst.
The electrocatalyst with the flower-like structure morphology structure synthesized by the method has higher specific surface area, and can improve the contact area of the electrocatalyst and reactants, thereby improving the catalytic reaction activity; the electrocatalyst with the flower-shaped structure also has structural rigidity, can provide a release space for a gas product generated in the reaction process, and can protect the structural stability of a catalytic material in the catalytic reaction generation process; on the basis of synthesizing a precursor material with a flower-shaped structure, a transition metal hydroxide or basic carbonate precursor is converted into a metal nitride active phase by regulating and controlling nitriding heat treatment conditions, so that the conductivity of the catalytic material is improved, the electron transmission process in the subsequent electrochemical reaction is promoted, and the intrinsic activity of the catalyst can be improved. In addition, the foamed nickel used as a carrier material has a porous network structure and good conductivity, the specific surface area of the catalytic material can be remarkably improved, and the mass transfer performance of the catalyst is further improved while more active sites are provided; and the electron/ion transmission resistance among the catalytic material, the electrolyte and the substrate in the electrocatalytic reaction process can be reduced, the conductivity of the catalyst is improved, and the catalytic performance of the catalyst is improved.
(2) The preparation method of the invention has the advantages of low cost of raw materials, convenient preparation and easy mass production.
(3) The catalyst provided by the invention has high intrinsic catalytic activity, abundant active sites and good conductivity, can efficiently and stably catalyze the electrochemical oxidation reaction of hydrazine under an alkaline condition, and has comprehensive catalytic performance at the top level of a reported hydrazine oxidation electrocatalyst.
Drawings
FIG. 1 shows a hydrothermal sample Ni obtained in example 1 of the present invention2Fe2X-ray diffraction patterns of CH/NF and series of nitriding heat-treated samples.
FIG. 2 shows Ni in a hydrothermal sample obtained in example 1 of the present invention2Fe2The polarization curve of the anodic oxidation reaction of the CH/NF and the hydrazine of the series of nitriding heat treatment samples in the solution containing 0.5M hydrazine monohydrate and 1.0M sodium hydroxide is compared.
FIG. 3 shows Ni in a hydrothermal sample obtained in example 1 of the present invention2Fe2CH/NF (a) and target sample Ni of nitriding heat treatment2Fe2Scanning electron topography of N/NF (b).
FIG. 4 shows Ni as a target sample of nitriding heat treatment obtained in example 1 of the present invention2Fe2A transmission electron microscope appearance picture (a) of N/NF; a selected area electron diffraction spectrum (b) and a high-resolution electron micrograph (c).
FIG. 5a shows a sample Ni of the hydrothermal sample obtained in example 1 of the present invention2Fe2CH/NF and nitriding heat treatment target sample Ni2Fe2And the full spectrum of the X-ray photoelectron spectrum of N/NF.
FIG. 5b is the bookHydrothermal sample Ni obtained in inventive example 12Fe2CH/NF and nitriding heat treatment target sample Ni2Fe2And the X-ray photoelectron spectrum of N/NF in the Ni 2p region.
FIG. 5c shows Ni in the hydrothermal sample obtained in example 1 of the present invention2Fe2CH/NF and nitriding heat treatment target sample Ni2Fe2An X-ray photoelectron spectrum of N/NF at Fe 2 p.
FIG. 5d shows Ni in the hydrothermal sample obtained in example 1 of the present invention2Fe2CH/NF and nitriding heat treatment target sample Ni2Fe2The X-ray photoelectron spectrum of N/NF in the N1s area.
FIG. 6a shows a sample Ni of the hydrothermal sample obtained in example 1 of the present invention2Fe2CH/NF and nitriding heat treatment target sample Ni2Fe2Comparison of the polarization curves of the anodic oxidation reaction of hydrazine in a solution containing 0.5M hydrazine monohydrate and 1.0M sodium hydroxide for N/NF and substrate NF.
FIG. 6b shows Ni in the hydrothermal sample obtained in example 1 of the present invention2Fe2CH/NF and nitriding heat treatment target sample Ni2Fe2N/NF and substrate NF under open circuit potential, the capacitance current density and potential sweep rate.
FIG. 6c shows Ni in the hydrothermal sample obtained in example 1 of the present invention2Fe2CH/NF and nitriding heat treatment target sample Ni2Fe2And the impedance spectrum test result graph of the N/NF and the substrate NF under the initial potential.
FIG. 7 shows Ni obtained in example 1 of the present invention2Fe2Durability test results of N/NF target samples (chronopotentiometry).
FIG. 8 shows Ni obtained in example 1 of the present invention2Fe2And (3) carrying out a scanning electron microscope topography under different multiples on the N/NF target sample after 120-hour durability test.
FIG. 9 shows Ni in a hydrothermal sample obtained in example 2 of the present invention3FeCH/NF and nitriding heat treatment sample Ni3X-ray diffraction pattern of FeN/NF.
FIG. 10 shows Ni in a hydrothermal sample obtained in example 2 of the present invention3FeCH/NF (a) and nitriding heat-treated sample Ni3Scanning electron topography of FeN/NF (b).
FIG. 11 shows Ni as a nitriding heat-treated sample obtained in example 2 of the present invention3Comparative plot of anodic oxidation reaction polarization curves of FeN/NF and substrate NF in solution containing 0.5M hydrazine monohydrate and 1.0M sodium hydroxide.
FIG. 12 shows a sample Ni obtained by nitriding heat treatment in example 3 of the present invention3X-ray diffraction pattern of N/NF.
FIG. 13 shows a sample Ni obtained by nitriding heat treatment in example 3 of the present invention3Polarization curves of N/NF and substrate NF hydrazine oxidation reaction are compared.
FIG. 14 shows a sample Fe of nitriding heat treatment obtained in example 4 of the present invention3X-ray diffraction pattern of N/NF.
FIG. 15 shows a sample Fe of nitriding heat treatment obtained in example 4 of the present invention3Polarization curves of N/NF and substrate NF hydrazine oxidation reaction are compared.
FIG. 16 is a schematic view of the preparation process of example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples and drawings, but the mode of carrying out the invention and the scope of protection are not limited thereto.
The preparation process of the present invention refers to the flowchart of fig. 16.
Example 1
Ni2Fe2Preparation of N/NF catalyst:
(1) foam Nickel (NF) is used as a carrier, the thickness of the foam Nickel (NF) is 1.60mm, and the surface density is 650g/m2The pore diameter is 0.20-0.80 mm. Mixing foamed nickel (1 × 4 cm)2) Ultrasonic cleaning with ethanol, hydrochloric acid solution (1M) and deionized water for 10 min, cleaning with deionized water, vacuum drying at 60 deg.C for 2 hr.
(2) Weighing 1mmol of nickel nitrate (Ni (NO)3)2·6H2O, 0.3g) and 1mmol of ferrous sulfate (FeSO)4·7H2O, 0.28g) was dissolved in a beaker containing 30mL of deionized water, a rotor was added and magnetic stirring was carried out at room temperature until a solution of 30mL of deionized water was obtainedAfter the solid particles were sufficiently dissolved, 5mmol of ammonium fluoride (NH) was added immediately4F, 0.19g) and 10mmol of Urea (0.6 g), taking out the rotor after the solution is clear and transparent by stirring, immediately transferring the reaction solution into a reaction kettle containing pretreated foamed nickel and having a volume of 50mL, carrying out hydrothermal reaction at 100 ℃ for 8 hours, naturally cooling to room temperature, then taking out the precursor loaded with the foamed nickel, carrying out sufficient ultrasonic cleaning for a plurality of times by water and ethanol, and placing at 60 ℃ for vacuum drying for 4 hours to obtain a hydrothermal sample Ni2Fe2CH/NF。
(3) After the hydrothermal sample is transversely placed in a quartz boat, the quartz boat is transferred into a tube furnace and placed in the right center of a furnace body, and the temperature of the furnace body is controlled at 60 ml/min of NH3an/Ar atmosphere (V)NH3/V Ar1/1) is heated to 450 ℃ at the heating rate of 5 ℃/min under the load, and then naturally cooled to room temperature after 3 hours of constant temperature nitriding heat treatment, thus obtaining the target sample Ni in the nitriding state2Fe2N/NF。
Changing the temperature of the nitriding heat treatment in the step (3) into: 300 ℃, 350 ℃, 380 ℃, 400 ℃, 500 ℃ and 600 ℃ to prepare corresponding series of nitriding heat treatment samples.
The X-ray diffraction patterns of the hydrothermal sample obtained in step (2) and the nitrided sample obtained in step (3) in this example are shown in FIG. 1. As can be seen from FIG. 1, the phase of the nitrided sample is related to the nitriding heat treatment temperature, and when the nitriding temperature is lower than 400 ℃, pure phase Ni is absent2Fe2N is generated; ni when the nitriding temperature is 600 ℃ or higher2Fe2The N phase may partially decompose and transform into the NiFe alloy phase.
The graphs of the hydrazine oxidation performance of the hydrothermal sample obtained in step (2) and the nitrided sample obtained in step (3) in this example are shown in fig. 2. From the results of fig. 2, it can be seen that the catalyst prepared by subjecting the hydrothermal sample to nitriding heat treatment at 450 ℃ has the best hydrazine oxidation performance, and the nitrided sample obtained at this temperature is the target sample.
The phase/structure/elemental chemical state characterization of the target catalyst (heat treatment at 450 ℃) obtained in this example:
in this example, Ni is a hydrothermal sample obtained in step (2)2Fe2CH/NF(a) And the target catalyst Ni obtained in the step (3)2Fe2The topography of the N/NF (b) is shown in FIG. 2.
In this example, Ni is a hydrothermal sample obtained in step (2)2Fe2CH/NF and the target catalyst Ni obtained in the step (3)2Fe2The X-ray diffraction pattern of N/NF is shown in FIG. 3.
FIG. 4 shows Ni as a target catalyst obtained in example 1 of step (3) of this example2Fe2Transmission electron micrograph of N/NF (a), target catalyst Ni2Fe2Selected area electron diffraction pattern (b) of N/NF, and target catalyst Ni2Fe2High resolution electron micrograph of N/NF (c).
FIG. 5 shows the samples Ni in the hydrothermal state obtained in steps (2) and (3) of this example2Fe2CH/NF and target catalyst Ni2Fe2X-ray photoelectron spectrum of N/NF: (a) a full spectrogram; (b) a Ni 2p spectrum; (c) fe 2p spectrum; (d) n1s spectrum.
(1) The observation by a scanning electron microscope (figure 2) shows that: through hydrothermal reaction treatment, a large amount of three-dimensional nanometer flower-shaped morphology structures formed by self-assembly of the nanometer sheets grow on the surface of the foamed nickel, and the surfaces of the nanometer sheets are smooth; after nitriding heat treatment at 450 ℃ for 3 hours, the flower-like structure is well maintained as a whole, but the originally smooth nanosheet structure becomes rough and porous.
(2) XRD analysis (figure 3) showed that: the phase structure of the hydrothermal sample is Ni2Fe2(CO3)(OH)8·2H2O, abbreviated as Ni2Fe2CH (CH); after nitriding heat treatment at 450 ℃ for 3 hours, Ni2Fe2Complete conversion of CH to Ni2Fe2An N nanocrystalline phase.
(3) Nitrided heat treated sample Ni obtained in this example2Fe2The transmission electron microscope topography (a), the selected region electron diffraction (b) and the high resolution electron microscope (c) of the N/NF are shown in FIG. 4. Transmission electron microscopy (a in fig. 4) further confirmed that the sample after heat treatment had a porous character; selective electron diffraction analysis (b in FIG. 4) confirmed Ni2Fe2Formation of N nanocrystal phase, observed by high resolution electron microscopy (c in FIG. 4), was further followedConfirming that the porous nano-component phase is Ni2Fe2And N crystal phase.
(4) Hydrothermal sample Ni obtained in this example2Fe2CH/NF and nitriding heat treatment sample Ni2Fe2The X-ray photoelectron spectrum of N/NF is shown in FIG. 4: (a) a full spectrogram; (b) a Ni 2p spectrum; (c) fe 2p spectrum; (d) n1s spectrum. As can be seen from FIG. 5, only Ni, Fe, C and O elements are present in the hydrothermal sample (a in FIG. 5), and both Ni and Fe elements are present in the oxidized state (b and C in FIG. 5). In addition to the existence of signals of Ni, Fe, C and O elements, the samples subjected to nitriding heat treatment can also find that the signal intensity of the O element is obviously reduced and a new N signal appears, which indicates that Ni is in the process of nitriding heat treatment2Fe2CH is reduced to a metal nitride. The Ni-N signal in fig. 5b, the Fe-N signal in fig. 5c and the N-M (M ═ Ni, Fe) signal in fig. 5d further confirm the formation of nickel iron nitride.
Target sample Ni obtained in this example2Fe2Electrocatalytic performance test of N/NF (heat treatment at 450 ℃):
(1) hydrothermal sample Ni obtained in this example2Fe2CH/NF and nitriding heat treatment sample Ni2Fe2A comparison of the anodic oxidation polarization curves of N/NF and substrate NF in a solution containing 0.5M hydrazine monohydrate and 1.0M sodium hydroxide is shown in FIG. 6 a. The results show that Ni2Fe2The N/NF sample has excellent hydrazine oxidation reaction electrocatalytic activity, and can reach 1017mA/cm when the potential is 0.3V relative to a reversible hydrogen electrode in a solution containing 0.5M hydrazine monohydrate and 1.0M sodium hydroxide2The current density of (1).
(2) Hydrothermal sample Ni obtained in this example2Fe2CH/NF and nitriding heat treatment sample Ni2Fe2The relationship between the capacitance current density and potential sweep rate of N/NF and substrate NF at open circuit potential is shown in FIG. 6 b. As can be seen from FIG. 6b, compared to Ni2Fe2The double electric layer capacitance of the sample obtained by nitriding heat treatment of the CH/NF hydrothermal precursor and the NF substrate for 3 hours at 450 ℃ is obviously increased, which reflects that the electrochemical specific surface area is obviously increased, and indicates that the nitriding heat treatment sample can reactAnd the number of active sites is obviously increased.
(3) Hydrothermal sample Ni obtained in this example2Fe2CH/NF and nitriding heat treatment sample Ni2Fe2The results of the impedance spectroscopy test of N/NF and substrate NF at the initial potential are shown in FIG. 6 c. As can be seen from FIG. 6c, compared to Ni2Fe2CH/NF hydrothermal precursor and NF substrate, Ni2Fe2The N/NF sample has obviously reduced charge transfer resistance and is derived from Ni2Fe2And (4) generating an N phase.
(4) Ni obtained in example2Fe2The durability test results for the N/NF samples are shown in FIG. 7. As a result, a constant current (10 mA/cm) was observed for 120 hours2Current density) test, Ni2Fe2The activity of the N/NF sample is not obviously degraded, which indicates that the catalyst has good durability.
(5) Ni obtained in example2Fe2The topography of the N/NF catalyst after 120 hours durability test is shown in FIG. 8. The result shows that the morphology and the characteristics of the hierarchical nano structure of the catalyst are not obviously changed, which indicates that the catalyst has good structural stability.
Example 2
Ni3Preparation of FeN/NF catalyst:
in the synthesis of example 2, only 1mmol of nickel nitrate (Ni (NO) was added3)2·6H2O, 0.3g) and 1mmol of ferrous sulfate (FeSO)4·7H2O, 0.28g) to 1.5mmol of nickel nitrate (Ni (NO)3)2·6H2O, 0.45g) and 0.5mmol of ferrous sulfate (FeSO)4·7H2O, 0.14g), the remaining preparation conditions correspond to those of example 1.
Phase/structure characterization of the catalyst:
hydrothermal sample Ni obtained in this example3FeCH/NF (a), Ni of nitriding heat treatment sample3The X-ray diffraction pattern of FeN/NF (b) is shown in FIG. 9. XRD analysis showed that: ni is generated in the hydrothermal reaction process6Fe2(CO3)(OH)16·4H2O, abbreviated as Ni3FeCH; performing nitriding heat treatment at 450 deg.C for 3 hrAfter aging, Ni3Complete conversion of FeCH to Ni3A FeN nanocrystalline phase.
Hydrothermal sample Ni obtained in this example3FeCH/NF (a), Ni of nitriding heat treatment sample3The SEM image of FeN/NF (b) is shown in FIG. 10. The observation of a scanning electron microscope shows that the sample after the nitriding heat treatment continues the nano flower-like structure of the hydrothermal sample, but the original sheet-like structure is converted into a porous structure formed by linking nano particles.
The target catalyst Ni obtained in this example3Testing the catalytic performance of FeN/NF:
nitrided sample Ni obtained in this example3FIG. 11 shows the polarization curve of hydrazine oxidation reaction of FeN/NF in comparison with that of foam nickel substrate. The test results show that Ni3The FeN/NF catalyst has excellent electrocatalytic activity of hydrazine oxidation reaction, and can reach 732mA/cm when the potential is 0.3V relative to a reversible hydrogen electrode in a solution containing 0.5M hydrazine monohydrate and 1M sodium hydroxide2The current density of (1).
Example 3
Ni3Preparation of N/NF catalyst:
in the synthesis of example 3, only 1mmol of nickel nitrate (Ni (NO) was added3)2·6H2O, 0.3g) and 1mmol of ferrous sulfate (FeSO)4·7H2O, 0.28g) to 2mmol of nickel nitrate (Ni (NO)3)2·6H2O, 0.6g), the nitriding heat treatment temperature was set to 350 ℃, and the other preparation conditions were the same as in example 1.
Ni3N/NF catalyst phase determination:
nitrided heat treated sample Ni obtained in this example3The X-ray diffraction pattern of N/NF is shown in FIG. 12. As can be seen from the figure, the catalyst phase obtained in this example was Ni3N。
The target catalyst Ni obtained in this example3N/NF catalysis performance test:
nitrided sample Ni obtained in this example3The polarization curve of the hydrazine oxidation reaction of N/NF is compared with that of the foam nickel substrate, and the graph is shown in FIG. 13. The test results show that Ni3N/NF catalystThe catalyst has excellent electrocatalytic activity of hydrazine oxidation reaction, and can provide up to 611mA/cm in a solution containing 0.5M hydrazine monohydrate and 1M sodium hydroxide when the potential is 0.3V relative to the reversible hydrogen electrode2The current density of (1).
Example 4
Fe3Preparation of N/NF catalyst:
in the synthesis of example 3, only 1mmol of nickel nitrate (Ni (NO) was added3)2·6H2O, 0.3g) and 1mmol of ferrous sulfate (FeSO)4·7H2O, 0.28g) to 2mmol of ferrous sulfate (FeSO)4·7H2O, 0.56g), the remaining preparation conditions correspond to those of example 1.
Fe3N/NF catalyst phase determination:
nitrided heat-treated sample Fe obtained in this example3The X-ray diffraction pattern of N/NF is shown in FIG. 14. As can be seen from the figure, the catalyst phase obtained in this example was Fe3N。
The target catalyst Fe obtained in this example3N/NF catalysis performance test:
nitrided sample Fe obtained in this example3The polarization curve of the hydrazine oxidation reaction of N/NF is compared with that of the foam nickel substrate, and the graph is shown in FIG. 15. The test result shows that Fe3The N/NF catalyst has excellent electro-catalytic activity of hydrazine oxidation reaction, and can only provide 45mA/cm in a solution containing 0.5M hydrazine monohydrate and 1M sodium hydroxide when the potential is 0.3V relative to the reversible hydrogen electrode2Current density of (B) indicates Fe3The oxidation activity of N-hydrazine is poor.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A monolithic transition metal nitride electrocatalyst with flower-like structure, characterized in that the electrocatalyst is composed of transition metal nitride and support material, the transition metal nitride is supported on the surface of the support material.
2. The monolithic transition metal nitride electrocatalyst with flower-like structure according to claim 1, wherein the transition metal nitride is the active phase; the transition metal refers to one or a combination of more of Ni, Co, Fe, Cu, W, Mo or Mn.
3. The monolithic transition metal nitride electrocatalyst with flower-like structure according to claim 1, wherein the transition metal nitride has flower-like morphology with diameter of 1-10 μ ι η; the flower-shaped structure is composed of nanosheets, and the thickness of each nanosheet is 1-50 nm.
4. The monolithic transition metal nitride electrocatalyst with flower-like structure according to claim 1, wherein the support material is selected from metal foam, metal mesh or porous carbon material with independent framework structure.
5. The method for preparing a monolithic transition metal nitride electrocatalyst with a flower-like structure according to any one of claims 1 to 4, comprising the steps of:
adding a carrier material into an aqueous solution containing a transition metal salt, a precipitator and a shape regulator, carrying out hydrothermal reaction at 80-180 ℃, growing a transition metal hydroxide or basic carbonate precursor with a flower-like structure on the surface of the carrier material, carrying out subsequent cleaning and drying, and carrying out nitriding heat treatment in a mixed atmosphere consisting of ammonia gas and inert gas at the temperature of 250-800 ℃ to obtain the integral transition metal nitride electrocatalyst with the flower-like structure.
6. The method for preparing monolithic transition metal nitride electrocatalyst with flower-like structure according to claim 5, wherein the transition metal salt is one or combination of several of halide, nitrate, sulfate, sulfamate, acetate of transition metal or other oxygen-containing or non-oxygen-containing acid salt of transition metal, and the concentration of transition metal ion in the aqueous solution is 0.0001-0.3M; the transition metal refers to one or a combination of more of Ni, Co, Fe, Cu, W, Mo or Mn.
7. The method for preparing the monolithic transition metal nitride electrocatalyst with a flower-like structure according to claim 5, wherein the precipitant is at least one of ammonia water, hexamethylenetetramine, dimethyl oxalate, diethyl oxalate, urea, and chloroethanol, and the concentration of the precipitant in the aqueous solution is 0.0001-0.6M.
8. The method for preparing a monolithic transition metal nitride electrocatalyst with flower-like structure according to claim 5, wherein the shape modifier is at least one of ammonium fluoride, sodium fluoride, calcium chloride, potassium chloride, and the concentration of the shape modifier in the aqueous solution is 0.0001-0.3M; the time of the hydrothermal reaction is 4-48 hours.
9. The method for preparing the monolithic transition metal nitride electrocatalyst with a flower-like structure according to claim 5, wherein the nitriding heat treatment time is 0.5-6 hours, and the temperature rise rate is 2-10 ℃/min; the nitriding heat treatment is carried out under the mixed atmosphere of ammonia gas and inert gas and under the load flow; the carrier gas carrier flow rate is 30-200 ml/min; the inert gas is argon; the volume ratio of ammonia gas to inert gas in the mixed atmosphere is 0.05-1: 1.
10. the monolithic transition metal nitride electrocatalyst with flower-like structure of any one of claims 1 to 4 applied as anode material in hydrazine hydrate fuel cell.
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