CN110280275B - Fe-doped trinickel selenide nanorod/nanosheet hierarchical array structure material, preparation method and application thereof - Google Patents
Fe-doped trinickel selenide nanorod/nanosheet hierarchical array structure material, preparation method and application thereof Download PDFInfo
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- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 abstract description 27
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- B01J35/33—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- 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
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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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- 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 a Fe-doped nickel selenide nanorod/nanosheet hierarchical array structure material, a preparation method and application thereof. The preparation method comprises the following steps: dissolving Se powder and a reducing agent in a mixed solution of ammonia water and deionized water, obliquely placing foamed nickel in the mixed solution, and carrying out hydrothermal reaction to obtain foamed nickel with a precursor; and dissolving iron salt in a mixed solution of ethanol and NaClO, adding foam nickel with a precursor, and carrying out solvothermal reaction to obtain a product. Compared with the prior art, the invention uses the low-temperature liquid phase synthesis method to synthesize Fe3+Ion doping to Ni3Se4In the crystal lattice of the hierarchical nano structure, the method is simple and the cost is low; the electrocatalyst has the advantages of large active area, good conductivity and the like when being used as an Oxygen Evolution Reaction (OER), a Hydrogen Evolution Reaction (HER) and a total hydrolysis reaction electrocatalyst; fe doped Ni3Se4The nano-rod/nano-sheet hierarchical array structure material can realize high-efficiency full-water decomposition under high current density, and shows excellent stability under low and high current densities.
Description
Technical Field
The invention belongs to the field of nano material preparation methods and electrocatalysis cross application, and particularly relates to a Fe-doped nickel selenide nano rod/nano sheet hierarchical array structure material, a preparation method and application thereof.
Background
Electrocatalytic water decomposition to produce clean and renewable fuels includes anodic Oxygen Evolution Reaction (OER) and cathodic Hydrogen Evolution Reaction (HER). Advances in this technology require active, stable, and inexpensive electrocatalysts to reduce overpotentials and accelerate OER and HER kinetics. The 3d transition metal compound is considered to be an ideal water decomposition electrocatalyst because good catalytic performance can be obtained by precisely controlling the composition and structure thereof. Among them, nickel-based compounds, such as nickel selenide, have a unique electronic structure, are inexpensive and readily available, and are being explored as OER and HER electrocatalysts.
However, the higher overpotential of the nickel selenide material during electrocatalytic water decomposition increases energy consumption, and the structure of the nickel selenide material is easy to change after long-term use, so that the practical application of the nickel selenide material in electrocatalytic water decomposition is limited. The heterogeneous cation doped nickel selenide can adjust the electronic structure of the nickel selenide, increase the exposed active sites and obviously improve the OER and total hydrolysis performance. In the selenide, Ni3Se4Than other selenides such as NiSe and NiSe2Has higher conductivity and potential of improving the electrocatalytic water decomposition activity. But with respect to chemically doped Ni3Se4There are few reports on the use of electrocatalytic total moisture decomposition. Therefore, a definite cation-doped Ni is elaborately constructed3Se4The nano structure, the controlled morphology and the electronic structure, the enhanced conductivity and the increased active site have important significance in realizing the outstanding electrocatalytic water decomposition activity and stability.
Disclosure of Invention
The invention aims to provide a Fe-doped nickel selenide (TRINi) nanorod/nanosheet hierarchical array structure material and a preparation method thereof3Se4The nano-rod/nano-sheet hierarchical array structure material has simple synthesis method and low cost.
The invention also provides Fe-doped Ni3Se4The nanorod/nanosheet hierarchical array structure material is applied as an electrocatalyst for Oxygen Evolution Reaction (OER), Hydrogen Evolution Reaction (HER) or total moisture decomposition reaction.
The present invention providesFe doped Ni3Se4The preparation method of the nano-rod/nano-sheet hierarchical array structure material comprises the following steps:
(1) dissolving Se powder and a reducing agent in a mixed solution of ammonia water and deionized water, carrying out ultrasonic stirring to obtain a solution A, then transferring the solution A into a reaction kettle, obliquely placing foamed nickel into the solution A, carrying out hydrothermal reaction, naturally cooling to room temperature, washing and drying to obtain foamed nickel with a precursor;
(2) dissolving iron salt in a mixed solution of ethanol and NaClO to obtain a solution B, transferring the solution B to a reaction kettle, obliquely placing the foamed nickel with the precursor prepared in the step (1) in the solution B, carrying out solvothermal reaction, naturally cooling to room temperature after the reaction is finished, washing and drying to obtain Fe-doped Ni3Se4A nano-rod/nano-sheet hierarchical array structure material.
Further, in the step (1), the ratio of the amounts of the Se powder and the reducing agent is 1: 2.3-2.8, preferably 1: 2.5.
The reducing agent is NaBH4(ii) a The iron salt is Fe (NO)3)3·9H2O。
In the step (1), the volume ratio of the ammonia water to the deionized water is 5-15: 35-25; the concentration of the selenium powder in the solution A is 20-30mM, and 25mM is preferred.
In the step (1), the hydrothermal reaction is carried out for 8-12h at 120 ℃, preferably for 8h at 120 ℃.
In the step (1), the foamed nickel needs to be cleaned before use, and the specific cleaning method comprises the following steps: soaking in 6M hydrochloric acid for 15min to remove the outer oxide film, cleaning with deionized water and anhydrous ethanol, and cutting into 2 × 3cm size.
In the step (1), the hydrothermal reaction is carried out in a stainless steel reaction kettle with a polytetrafluoroethylene lining; the washing is as follows: washing with deionized water for 3-5 times, and washing with anhydrous ethanol for 3-5 times; the drying comprises the following steps: drying in a vacuum drying oven at 55-60 deg.C for 6-12 h.
In the step (2), the concentration of the iron salt in the solution B is 20-30mM, and preferably 25.8 mM.
In the step (2), the volume ratio of the ethanol to the NaClO is 150-180: 1, preferably 160: 1.
In the step (2), the solvent thermal reaction is carried out for 4-8h at 140 ℃, preferably for 6h at 140 ℃.
In the step (2), the solvothermal reaction is carried out in a stainless steel reaction kettle with a polytetrafluoroethylene lining; the washing is as follows: washing with deionized water for 3-5 times, and washing with anhydrous ethanol for 3-5 times; the drying comprises the following steps: drying in a vacuum drying oven at 55-60 deg.C for 6-12 h.
The invention also provides Fe-doped Ni prepared by the preparation method3Se4A nano-rod/nano-sheet hierarchical array structure material, the Fe is doped with Ni3Se4The shape of the nano-rod/nano-sheet hierarchical array structure material is that nano-sheets with the transverse size of 180-200nm grow on nano-rods with the average diameter of 50-70 nm.
The invention also provides the Fe-doped Ni3Se4The nanorod/nanosheet hierarchical array structure material is applied as an electrocatalyst for Oxygen Evolution Reaction (OER) or Hydrogen Evolution Reaction (HER) or total water decomposition reaction.
The Fe is doped with Ni3Se4When the nanorod/nanosheet hierarchical array structure material is applied as an electrocatalyst for Oxygen Evolution Reaction (OER) or Hydrogen Evolution Reaction (HER), the specific method comprises the following steps: doping Ni with said Fe3Se4The nanorod/nanosheet hierarchical array structure material is used as a working electrode, a platinum wire (OER reaction) or a carbon rod (HER reaction) and an Ag/AgCl electrode are used as a counter electrode and a reference electrode respectively, an electrolyte is a 1.0M KOH solution, and electrochemical testing is performed by using a CHI760E electrochemical workstation. Linear scanning polarization curve (LSV) at 2.0mV · s-1Is performed at a scan rate of 90% ohmic compensation. Stability was obtained by measuring the current density time curve at constant voltage. Electrochemically active area (ECSA) was determined by scanning (2, 4, 6, 8, 10 and 12mV · s) at different scan rates without significant faraday region-1) Cyclic voltammetry measurement of electrochemical double layer capacitance (C)dl) Carrying out evaluation; electrochemical Impedance (EIS) is open-circuited in a frequency range of 100kHz to 0.1HzThe voltage was tested. In the commercial RuO2And Pt/C supported on nickel foam as electrodes, OER and HER performance were tested separately for comparison.
The Fe is doped with Ni3Se4When the nanorod/nanosheet hierarchical array structure material is applied as an electrocatalyst for full-water decomposition reaction, the specific method comprises the following steps: doping Ni with said Fe3Se4The nanorod/nanosheet hierarchical array structure material is assembled in a double-electrode electrolytic cell as an anode and a cathode respectively, and a linear scanning polarization curve (LSV) under 90% ohm compensation and the current density time stability under constant voltage are tested. As a comparison, the noble metal RuO supported on nickel foam in a two-electrode electrolyzer was investigated2LSV polarization curves as anode and Pt/C as cathode.
The Fe doped Ni provided by the invention3Se4The nano-rod/nano-sheet hierarchical array structure material is Fe-doped with Ni3Se4The conductivity and mass transfer behavior of the material are significantly enhanced. Fe3+Ion doping into Ni3Se4The crystal lattice can expose larger catalytic activity sites, the actual contact interface area between the crystal lattice and the electrolyte is increased, the rapid interface charge transfer is ensured, and the electrocatalytic reaction is facilitated. The metal cations are overlapped through d-d orbitals inside the crystal lattice to realize the delocalization of charges, improve the Lewis acidity, promote the adsorption and activation of water, increase the electrophilicity of adsorbed oxygen, form O-OH species through nucleophilic attack, and generate O through deprotonation by an electron-withdrawing induction effect2. Charge delocalization between cations provides a donor-acceptor chemisorption site for reversible adsorption of oxygen, which is beneficial to OER catalytic reaction. In strong alkaline electrolyte, a surface oxide layer or a surface hydroxide layer is formed on the surface of the catalyst in the electrolytic process and is the actual active site, and Fe with higher conductivity under the surface is doped with Ni3Se4The nanorod/nanosheet hierarchical structure can accelerate electron transfer between the electrode and the metal oxide or metal hydroxide shell. Meanwhile, the thin oxide shell or hydroxide shell on the surface can be used as a protective layer to stabilize Fe doped Ni3Se4Nano meterRod/nanosheet hierarchical structures. The in-situ formed large amount of solid-solid interfaces promote the chemical adsorption of oxygen and hydrogen intermediates, so that the OER activity and the HER behavior can be improved, and the full-water electrolysis electrocatalytic performance is excellent.
Compared with the prior art, the method uses NaBH by a simple chemical liquid phase method4Reduction of Se powder to form Se2-The ions react with Ni on the surface of the foam nickel to generate NiSe seeds, and under the coordination action of ammonia water molecules, the NiSe seeds grow in an oriented mode to obtain the nickel selenide nanorod precursor. Further ClO-Ionic bonding of Ni in NiSe2+Partial oxidation to Ni3+Formation of Ni3Se4The nano-rod is partially dissolved and epitaxially grown into a nano-sheet structure and Fe3+Ion coupling into Ni3Se4In the crystal lattice, Fe is synthesized in situ3+Ion-doped Ni3Se4A nano-rod/nano-sheet hierarchical array structure. The application of the OER, HER and full-moisture decomposition electrocatalyst materials provided by the invention has the characteristics of low overpotential under high current density, good stability, environment-friendly and simple preparation process and low cost.
Drawings
FIG. 1 is an X-ray powder diffraction (XRD) pattern of a precursor NiSe nanorod array structure material prepared in example 1;
FIG. 2 shows Fe-doped Ni prepared in example 13Se4An X-ray powder diffraction (XRD) pattern of the nano-rod/nano-sheet hierarchical array structure material;
FIG. 3 is a Scanning Electron Microscope (SEM) image of a precursor NiSe nanorod array structure material prepared in example 1;
FIG. 4 shows Fe-doped Ni prepared in example 13Se4A Scanning Electron Microscope (SEM) image of the nanorod/nanosheet hierarchical array structure material;
FIG. 5 shows Fe-doped Ni prepared in example 13Se4Energy dispersive X-ray (EDX) spectroscopy of nanorod/nanosheet hierarchical array structure materials;
FIG. 6 shows Fe-doped Ni prepared in example 13Se4Nanorod/nanosheet fractionationA Transmission Electron Microscope (TEM) image of the array structure material;
FIG. 7 shows Fe-doped Ni prepared in example 13Se4High resolution lattice fringe (HRTEM) images of nanorod/nanosheet hierarchical array structure materials;
FIG. 8 is a Scanning Electron Microscope (SEM) picture of the Fe-doped NiSe nanorod array structure material prepared in comparative example 1;
FIG. 9 shows Fe-doped Ni prepared in example 13Se4OER polarization curves for the nanorod/nanosheet hierarchical array structure and the Fe-doped NiSe nanorod array structure prepared in comparative example 1.
FIG. 10 shows Fe-doped Ni prepared in example 13Se4HER polarization curves for the nanorod/nanosheet hierarchical array structure and the Fe-doped nisi nanorod array structure prepared in comparative example 1.
FIG. 11 shows the doping of Fe with Ni in example 23Se4Linear polarization curve diagram (the insets are polarization curves under high current density) of the nanorod/nanosheet hierarchical array structure material OER;
FIG. 12 shows the doping of Fe with Ni in example 23Se4A current density time curve graph of the nanorod/nanosheet hierarchical array structure material OER;
FIG. 13 shows the doping of Fe with Ni in example 23Se4A capacitance-current diagram of the nano-rod/nano-sheet hierarchical array structure material under different sweep speeds;
FIG. 14 shows the doping of Fe with Ni in example 23Se4Impedance diagram of nano-rod/nano-sheet hierarchical array structure material;
FIG. 15 shows the doping of Fe with Ni in example 33Se4Linear polarization curve diagram (the insets are polarization curves under high current density) of the nanorod/nanosheet hierarchical array structure material HER;
FIG. 16 shows the doping of Fe with Ni in example 33Se4A current density time curve graph of a nanorod/nanosheet hierarchical array structure material HER;
FIG. 17 shows the doping of Fe with Ni in example 43Se4Total water content of nano-rod/nano-sheet hierarchical array structure material in two-electrode systemPolarization plot of the solution (inset is polarization curve at high current density);
FIG. 18 shows the doping of Fe with Ni in example 43Se4A current density time curve graph of the total water decomposition of the nano-rod/nano-sheet hierarchical array structure material in a two-electrode system;
FIG. 19 shows the doping of Fe with Ni in example 53Se4The nano-rod/nano-sheet hierarchical array structure material is driven by a section of 1.5V dry battery (the inset is an enlarged diagram of two electrodes).
Detailed Description
The invention is described in detail below with reference to the following examples and the accompanying drawings.
Example 1
Fe-doped Ni3Se4The preparation method of the nano-rod/nano-sheet hierarchical array structure material comprises the following steps:
(1) a piece of Nickel Foam (NF) with an area of 2 x 3cm is put into 6M hydrochloric acid to be soaked for 15min, and then the piece of Nickel Foam (NF) is washed 3 times by deionized water and absolute ethyl alcohol respectively. Measuring 15mL of ammonia water, adding the ammonia water into 25mL of deionized water, uniformly stirring, and accurately weighing 1mmol of Se powder and 2.5mmol of NaBH4Adding the mixed solution, performing ultrasonic stirring for 30min, transferring the reddish brown solution into a stainless steel reaction kettle with a lining made of 50mL polytetrafluoroethylene, obliquely putting the pretreated foamed nickel into the solution, and reacting in an oven at 120 ℃ for 8 h. Naturally cooling to room temperature after the reaction is finished, and covering the black sample with foam nickel A1And (3) washing the sample with deionized water and absolute ethyl alcohol respectively, and drying the obtained precursor sample in a vacuum drying oven at 60 ℃ for 10 hours.
(2) Firstly, measuring 40mL of absolute ethyl alcohol, adding the absolute ethyl alcohol into a clean small beaker, then transferring 0.25mL of sodium hypochlorite solution, adding the sodium hypochlorite solution into the absolute ethyl alcohol, and uniformly stirring; 1mmol of Fe (NO) was weighed3)3·9H2Adding O into the mixed solution, stirring to dissolve, transferring the solution into a stainless steel reaction kettle with a lining of 50mL polytetrafluoroethylene, and then adding foamed nickel A1Put into the solution obliquely and react for 8h in an oven at 140 ℃. Naturally cooling to room temperature after the reaction is completed, and using deionized water and anhydrous ethyl alcohol to cover the foamed nickel of the sampleEach alcohol washing was performed 3 times to obtain sample A2Drying in a vacuum drying oven at 60 deg.C for 10h to obtain Fe-doped Ni3Se4A nano-rod/nano-sheet hierarchical array structure material.
Structural and morphological characterization of the product:
the phase identification of the precursor and the final product obtained in example 1 was performed by X-ray powder diffractometry (XRD), as shown in fig. 1 and 2, respectively. FIG. 1 shows that the precursor is a mixed phase of hexagonal phase NiSe (JCPDS No.75-0610) and orthogonal phase NiSe (JCPDS No. 29-0935). FIG. 2 shows that all diffraction peaks and monoclinic Ni on the final product3Se4Anastomosis (JCPDS No. 18-0890).
The precursor and the final product obtained in example 1 were analyzed by Scanning Electron Microscopy (SEM) for morphology, as shown in fig. 3 and 4, respectively. Fig. 3 shows that the precursor is in a nanorod array structure, and fig. 4 shows that the final sample is in a nanorod/nanosheet hierarchical structure with uniform size and uniform distribution.
The final product composition was analyzed using energy dispersive X-ray (EDX) spectroscopy. As shown in fig. 5, Fe element was successfully coupled into the sample, and the doping amount of Fe element was calculated to be 4.6% in terms of atomic percentage.
The Transmission Electron Microscope (TEM) image of the final product is shown in FIG. 6, which shows that the diameter of the nano-rod is 50-70nm, and the transverse dimension of the nano-sheet is 180-200 nm.
The High Resolution Transmission Electron Microscope (HRTEM) image of the final product is shown in FIG. 7, with an interplanar spacing of 0.22nm, corresponding to Ni3Se4The (211) plane of (a).
Comparative example 1
(1) 1mmol of Se powder and 2.5mmol of NaBH4Dissolving in a mixed solution of 15mL of ammonia water and 25mL of deionized water, carrying out ultrasonic stirring for 30min to obtain a solution A, transferring the solution A into a 50mL stainless steel reaction kettle with a polytetrafluoroethylene lining, obliquely placing foamed nickel into the solution A, and reacting in an oven at 120 ℃ for 8 h. Naturally cooling to room temperature after the reaction is finished, and covering the black sample with foam nickel A1Washing with deionized water and anhydrous ethanol for 3 times respectively to obtain precursor sample, and vacuum dryingDrying at 60 deg.C for 10 h;
(2) 1mmol of Fe (NO)3)3·9H2Dissolving O in 40mL of absolute ethanol to obtain a solution B, transferring the solution B to a stainless steel reaction kettle with a lining of 50mL of polytetrafluoroethylene, obliquely placing the foamed nickel with the precursor prepared in the step (1) in the solution B, reacting in an oven at 140 ℃ for 8h, naturally cooling to room temperature after the reaction is finished, washing, and drying to obtain the Fe-doped NiSe nanorod array structure material.
The final product obtained in comparative example 1 was subjected to morphological analysis by Scanning Electron Microscopy (SEM). FIG. 8 shows that the final product is a nanorod array structure.
FIG. 9 shows Fe-doped Ni obtained in example 13Se4OER polarization curves of the nanorod/nanosheet hierarchical array structure and the Fe-doped NiSe nanorod array structure obtained in comparative example 1. Indicating Fe doping with Ni3Se4The sample is superior to the Fe-doped NiSe sample.
FIG. 10 shows Fe-doped Ni obtained in example 13Se4OER polarization curves of the nanorod/nanosheet hierarchical array structure and the Fe-doped NiSe nanorod array structure obtained in comparative example 1. Indicating Fe doping with Ni3Se4The sample is superior to the Fe-doped NiSe sample.
Example 2
Fe-doped Ni3Se4The nano-rod/nano-sheet hierarchical array structure material is applied as an Oxygen Evolution Reaction (OER) catalyst.
The specific application method comprises the following steps: using Fe doped Ni with area of 0.5X 0.5cm3Se4The nano-rod/nano-sheet hierarchical array structure material is used as a working electrode, and a platinum wire and an Ag/AgCl electrode are respectively used as a counter electrode and a reference electrode. Electrochemical tests were performed in a 1.0M KOH electrolyte solution using CHI760E electrochemical workstation at room temperature (25 ℃). In the commercial RuO2The OER performance was compared on a load electrode basis. Linear Sweep Voltammetry (LSV) at 2.0mV · s-1And the polarization curve was obtained at 90% ohmic compensation. As shown in FIG. 11, Fe was doped with Ni3Se4The nano-rod/nano-sheet hierarchical array structure has obvious OER activityThe overpotential is as low as 220mV to reach 100mA cm-2Current density of (a) to NiSe nanorods (which are precursors prepared in step (1) of example 1) and commercial RuO, respectively2The overpotential of the catalyst is 99mV and 73mV less; in addition, Fe is doped with Ni3Se4The hierarchical array structure of the nano-rod/nano-sheet can reach 500mA cm under overpotential with relatively small 253mV and 264mV-2And 800mA · cm-2High current density. FIG. 12 is a graph of current density versus time showing Fe doping with Ni3Se4The nanorod/nanosheet hierarchical array structure shows good stability under low and high current densities, and the current density is kept above 96.8% after 11h of test. FIG. 13 is a graph of capacitance current at different scan rates, showing Fe doping with Ni3Se4The electric double layer capacitance was 3.4 mF. cm-21.9 mF.cm greater than NiSe-2Thus Fe is doped with Ni3Se4Has a larger electrochemical active area. FIG. 14 is an Electrochemical Impedance (EIS) diagram showing Fe doped Ni3Se4The semi-circle diameter of the nano rod/nano sheet hierarchical array structure is small, the slope of the straight line is large, and the nano rod/nano sheet hierarchical array structure is low in resistance and has quicker catalytic kinetics.
Example 3
Fe-doped Ni3Se4The nanorod/nanosheet hierarchical array structure material is applied as a Hydrogen Evolution Reaction (HER) catalyst.
The specific application method comprises the following steps: using Fe doped Ni with area of 0.5X 0.5cm3Se4The nano-rod/nano-sheet hierarchical array structure material is used as a working electrode, and a carbon rod and an Ag/AgCl electrode are respectively used as a counter electrode and a reference electrode. Electrochemical tests were performed in a 1.0M KOH electrolyte solution using CHI760E electrochemical workstation at room temperature (25 ℃). Linear Sweep Voltammetry (LSV) at 2.0mV · s-1And ohmic compensation of 90%. As shown in FIG. 15, Fe was doped with Ni3Se4The nanorod/nanosheet hierarchical array structure has excellent HER activity, and can reach 10 mA-cm only at a low potential of 153mV-2The current density of the NiSe nanorod is better than that of 182mV of the NiSe nanorod. Although commercial Pt/C electrodes are operated at low current densitiesHas lower overpotential, but under high current density, the material is easy to fall off to influence the activity. In addition, Fe is doped with Ni3Se4The hierarchical array structure of the nano-rod/nano-sheet can reach 100mA cm under the overpotential with quite small values of 233mV and 269mV-2And 500mA · cm-2High current density. FIG. 16 is a graph of current density versus time showing Fe doping with Ni3Se4The nanorod/nanosheet hierarchical array structure shows excellent stability under low and high current densities, and the current density is kept above 96.2% after 11h of test.
Example 4
Fe-doped Ni3Se4The nano-rod/nano-sheet hierarchical array structure material is applied as an all-water decomposition reaction electrocatalyst.
The specific application method comprises the following steps: 2 Fe areas of 0.5X 0.5cm were doped with Ni3Se4The nano-rod/nano-sheet hierarchical array structure material is respectively used as a cathode and an anode to be assembled in a double-electrode electrolytic cell, and the full-water decomposition performance is tested in a 1.0M KOH electrolyte solution. Linear Sweep Voltammetry (LSV) at 2.0mV · s-1And the polarization curve was obtained at 90% ohmic compensation. As shown in FIG. 17, Fe was doped with Ni3Se4The nano-rod/nano-sheet hierarchical array structure material has excellent electrocatalytic full-water decomposition activity, and can reach 10 mA-cm under the voltage of 1.58V-2The current density of (2) is only 1.94V required to drive 500mA cm-2High current density. Despite the commercial RuO2The electric couple composed of Pt and C has slightly high activity under low current density, but can not reach 500mA cm because the material is easy to fall off-2High current density. FIG. 18 is a graph of current density versus time showing Fe doping with Ni3Se4The nanorod/nanosheet hierarchical array structure shows good stability under low and high current densities, and the current density is kept above 93.5% after 11h of test.
Example 5
Fe prepared by the invention is doped with Ni3Se4The nano-rod/nano-sheet hierarchical array structure material is cut into 2 pieces with the size of 1 multiplied by 1cm and divided intoThe cathode and anode were assembled in an electrolytic cell with 1.0MKOH electrolyte solution, and operated with a 1.5V dry cell, the results are shown in FIG. 19. Bubbles can be continuously generated on the two electrodes, which proves that Fe is doped with Ni3Se4The nano-rod/nano-sheet hierarchical array structure material can continuously drive the full water decomposition by using low voltage.
The above detailed description of Fe-doped trinickel selenide nanorod/nanosheet hierarchical array structure material, the preparation method and the application thereof with reference to the embodiments are illustrative and not restrictive, and several embodiments can be enumerated within the limited scope, so that changes and modifications without departing from the general concept of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. Fe-doped Ni3Se4The preparation method of the nano-rod/nano-sheet hierarchical array structure material is characterized by comprising the following steps:
(1) dissolving Se powder and a reducing agent in a mixed solution of ammonia water and deionized water, carrying out ultrasonic stirring to obtain a solution A, then transferring the solution A into a reaction kettle, obliquely placing foamed nickel into the solution A, sealing, carrying out heating reaction, naturally cooling to room temperature after the reaction is finished, washing and drying to obtain foamed nickel with a precursor;
(2) dissolving iron salt in a mixed solution of ethanol and NaClO to obtain a solution B, transferring the solution B to a reaction kettle, obliquely placing the foamed nickel with the precursor prepared in the step (1) in the solution B, sealing, heating for reaction, naturally cooling to room temperature after the reaction is finished, washing and drying to obtain Fe-doped Ni3Se4A nano-rod/nano-sheet hierarchical array structure material.
2. The production method according to claim 1, wherein in step (1), the ratio of the amounts of the Se powder and the reducing agent is 1: 2.3-2.8.
3. The method of claim 1, wherein the method further comprisesThe original agent is NaBH4(ii) a The iron salt is Fe (NO)3)3·9H2O。
4. The method according to any one of claims 1 to 3, wherein in the step (1), the volume ratio of the ammonia water to the deionized water is 5-15: 35-25; the concentration of the selenium powder in the solution A is 20-30 mM.
5. The production method according to any one of claims 1 to 3, wherein in the step (1), the heating reaction is carried out at 120 ℃ for 8 to 12 hours.
6. The method according to any one of claims 1 to 3, wherein the concentration of the iron salt in the solution B in the step (2) is 20 to 30 mM.
7. The method according to any one of claims 1 to 3, wherein in the step (2), the volume ratio of the ethanol to the NaClO is 150 to 180: 1.
8. The method according to claim 1, wherein in the step (2), the heating reaction is carried out at 140 ℃ for 4-8 h.
9. Fe-doped Ni prepared by the preparation method of any one of claims 1 to 83Se4A nano-rod/nano-sheet hierarchical array structure material.
10. Fe doped Ni according to claim 93Se4The nanorod/nanosheet hierarchical array structure material is applied as an electrocatalyst for Oxygen Evolution Reaction (OER) or Hydrogen Evolution Reaction (HER) or total water decomposition reaction.
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| CN111020626B (en) * | 2019-12-09 | 2021-03-16 | 北京工业大学 | Preparation method and application of nickel-molybdenum oxide with 3D nanosheet-nanorod mixed structure |
| CN113512738B (en) * | 2021-06-24 | 2022-07-05 | 湖南师范大学 | Ternary iron-nickel-molybdenum-based composite material water electrolysis catalyst, and preparation method and application thereof |
| CN113789535B (en) * | 2021-10-09 | 2022-11-01 | 华中科技大学 | Rod-shaped ruthenium particle/selenide composite catalyst and preparation method and application thereof |
| CN114016073B (en) * | 2021-10-25 | 2023-12-19 | 吉林师范大学 | Fe doped Ni 0.85 Preparation method of Se nano sheet array electrocatalyst |
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