CN107904614B - A kind of Ni3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode and the preparation method and application thereof - Google Patents

A kind of Ni3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode and the preparation method and application thereof Download PDF

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CN107904614B
CN107904614B CN201710967077.XA CN201710967077A CN107904614B CN 107904614 B CN107904614 B CN 107904614B CN 201710967077 A CN201710967077 A CN 201710967077A CN 107904614 B CN107904614 B CN 107904614B
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electrode
ldh
preparation
oxygen
reaction kettle
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CN107904614A (en
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张果戈
袁俊逸
徐小兵
李文芳
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South China University of Technology SCUT
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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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/26—Anodisation of refractory metals or alloys based thereon
    • 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 kind of Ni3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode and the preparation method and application thereof, belongs to electrolysis elutriation oxygen catalytic field.The preparation method the following steps are included: Ni substrate pretreatment, the Ni-based anode oxidation membrane of growth in situ is prepared by the anodic oxidation of Ni substrate；Using Ni-based anode oxidation membrane as presoma, the Ni of nano bar-shape structure is obtained through vulcanization hydro-thermal3S2Film layer；Film layer after vulcanizing treatment is carried out to mix molten iron heat, obtains Ni3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode.The method of the present invention is novel, and it is convenient to operate, low in cost, is suitble to industrial production, the Ni of preparation3S2@Ni-Fe LDH electrode material is used for electrolysis water oxygen evolution reaction, and catalytic activity is high, and stability is good, can be used for industrializing electrolysis water production.

Description

A kind of Ni3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode and the preparation method and application thereof
Technical field
The present invention relates to electro-catalysis and electrolysis water field, in particular to a kind of Ni3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode And the preparation method and application thereof.
Background technique
Since fossil fuel faces exhaustion and there are problem of environmental pollution, the new energy of exploitation substitution conventional fossil fuel It is very necessary.The new energy being widely studied at present has solar energy, wind energy, nuclear energy, Hydrogen Energy, and wherein solar energy and wind energy are by day Gas influences greatly, and source is unstable, and nuclear energy has hidden danger caused by leakage.And Hydrogen Energy is easy to use, energy completely pollution-free to environment Metric density is high, and utilization efficiency is high, becomes the hot spot of new energy area research.
In current hydrogen preparation technique, water electrolysis hydrogen production is that a kind of application is relatively wide, method of technology maturation.Industry at present On the electrolyzed alkaline water method voltage that uses much higher than theoretical voltage, at least 25% power consumption for overcoming overpotential, The excessively high overpotential of Anodic oxygen evolution reaction is principal element, therefore developing efficient, stable oxygen-separating catalyst is electrolysis water row The problem of industry urgent need to resolve.
Traditional oxygen-separating catalyst is noble metal and its oxide (IrO2, RuO2 etc.), and catalytic performance is excellent, but price High, scarcity of resources makes it be difficult to large-scale application.Nickel and its compound show good analysis oxygen in the alkaline electrolyte and urge Change performance, and from a wealth of sources, low in cost, it is considered to be the good alternative materials of noble metal-based catalysts.
In the research of Ni-based oxygen-separating catalyst, surface microscopic topographic and electronic structure have decisive action to catalytic activity.Material Expect that making Nano surface and Fe element doping have been demonstrated that the catalytic active of nickel base electrode can be effectively improved, Ni-Fe LDH is recognized To be most potential Ni-based analysis oxygen catalysis material.A large amount of research, which efforts be made so that, has various nanometers with different method preparations The Ni-Fe LDH of pattern, such as electrodeposition process, chemical deposition, template, sol-gal process etc..The above method achieves centainly Achievement, but the nickel-base catalyst of most method preparation and the binding force of matrix be not high, holds in prolonged oxygen evolution reaction It easily falls off from matrix, influences the efficiency of electrolysis water；On the other hand, the Ni-Fe LDH of nanosizing is easy to roll into a ball in the synthesis process It is poly-, it is unfavorable for exposing more active sites.
Summary of the invention
For overcome the deficiencies in the prior art, the present invention provides a kind of Ni with core@shell structure3S2@Ni‐Fe LDH Oxygen electro catalytic electrode and the preparation method and application thereof is analysed, i.e., by anodizing and hydro-thermal method, prepares composite construction Ni3S2@Ni-Fe LDH material, analyses oxygen catalytic activity to it, analyses oxygen catalytic stability, AC impedance, gas evolution ability etc. into Detailed characterization is gone.The result shows that this analysis oxygen catalysis electrode has excellent analysis oxygen catalytic performance and good stability.
The invention is realized by the following technical scheme.
A kind of Ni3S2The preparation method of@Ni-Fe LDH analysis oxygen electro catalytic electrode, comprising the following steps:
(1) Ni substrate is immersed in electrolyte, carries out constant pressure anodized using three electrodes；
(2) gained sample after step (1) processing and vulcanization hydrothermal solution are added in hydrothermal reaction kettle and carry out vulcanization hydro-thermal Processing, is rinsed with water completely after processing, and drying obtains nano bar-shape Ni3S2Film layer；
(3) by nano bar-shape Ni obtained by step (2)3S2Film layer with mix molten iron hot solution be added hydrothermal reaction kettle in mixed Molten iron heat treatment, is rinsed with water completely after processing, and drying obtains Ni3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode.
Preferably, electrolyte used in step (1) described anodized contain 0.5~2wt% ammonium fluoride and The phosphoric acid of 75~85wt%.
Preferably, step (1) described anodized uses platinum electrode as to electrode, and saturated calomel electrode is as ginseng Compare electrode.
Preferably, the constant pressure current potential of step (1) described anodized is 3~5V, and the temperature of electrolyte is 15~35 DEG C, the time of anodic oxidation is 5~10 minutes.
Preferably, the filling rate of step (2) described hydrothermal reaction kettle is 40%~50%；It is described vulcanization hydro-thermal temperature be 100 DEG C~140 DEG C, the time is 6~12 hours.
Preferably, the vulcanized sodium containing 0.02~0.05mol/L in step (2) the vulcanization hydrothermal solution, 0.1~ The ammonium fluoride of 0.2mol/L and the ethyl alcohol of 5~12mol/L.
Preferably, the filling rate of step (3) described hydrothermal reaction kettle is 40%~50%；The temperature for mixing molten iron heat is 110 DEG C~120 DEG C, the time is 3~8 hours.
Preferably, step (3) ferric trichloride mixed in molten iron hot solution containing 0.5~2mmol/L, 0.1~1mol/ The ammonium fluoride of L and the neopelex of 0.1mol/L~0.5mol/L.
A kind of Ni being prepared by above-described preparation method3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode.
A kind of above-described Ni3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode urging as anode of electrolytic water oxygen evolution reaction Polarizing electrode.
Compared with existing analysis oxygen catalytic electrode material, the invention has the following advantages that
(1) Ni of the invention3S2The analysis oxygen catalytic performance that@Ni-Fe LDH analyses oxygen electro catalytic electrode is high, reaches 10mA/cm2 Overpotential needed for current density only has 245mV.
(2) Ni of the invention3S2@Ni-Fe LDH analysis oxygen electro catalytic electrode is with good stability, is analysing for a long time Oxygen is catalyzed in reaction test, through 10mA/cm2Current density constant current 40 hours, overpotential was held essentially constant, and had excellent electricity Chemical stability and mechanical stability.
(3) Ni of the invention3S2@Ni-Fe LDH analyse oxygen electro catalytic electrode growth in situ on metal Ni substrate, film layer with There is good binding force and electric conductivity between matrix, can directly be used in the case where not adding conductive agent or bonding agent, both The preparation step for simplifying electrode in turn avoids the problem of catalytic activity brought by the addition of inert matter declines.
(4) Ni-Fe LDH catalyst of the invention is carried on nano bar-shape Ni3S2On, due to Ni3S2With better than nickel Oxide/hydroxide electric conductivity, therefore electronics can be transmitted quickly in the electrodes, improve oxygen evolution reaction rate； Based on the bigger serface of nano bar-shape structure, Ni-Fe LDH catalyst can be uniformly distributed in Ni3S2On nanometer rods, solve Ni-Fe LDH is easy to the problem of reuniting, while having increased considerably the specific surface area of catalyst, the more active sites of exposure with Electrolyte solution contacts.
(5) raw material sources of the invention are extensive, low in cost, simple process, and it is convenient to operate, the electrode analysis oxygen catalysis of preparation Performance is high, and stability is strong, can be used for being electrolysed elutriation oxygen catalytic field.
Detailed description of the invention
Figure 1A is Ni3S2@Ni-Fe LDH analyses the SEM figure of oxygen electro catalytic electrode.
Figure 1B is the SEM figure of comparative sample 1.
Fig. 2A is Ni3S2@Ni-Fe LDH analyses the TEM figure of oxygen electro catalytic electrode.
Fig. 2 B is the TEM figure of comparative sample 1.
Fig. 3 A is Ni3S2The XRD diagram of@Ni-Fe LDH analysis oxygen electro catalytic electrode.
Fig. 3 B is the XRD diagram of comparative sample 1.
Fig. 4 A is Ni3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode and the nickel element XPS of comparative sample 1 schemes, and Fig. 4 B is Ni3S2
@Ni-Fe LDH analyses the ferro element XPS figure of oxygen electro catalytic electrode.
Fig. 5 is Ni3S2The Raman spectrogram of@Ni-Fe LDH analysis oxygen electro catalytic electrode.
Fig. 6 is Ni3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode and comparative sample 1, IrO2The electrolysis of/C electrode, pure nickel piece Elutriation oxygen catalytic performance test CV figure.
Fig. 7 A is Ni3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode and IrO2The electrolysis elutriation oxygen catalysis of/C electrode is long-term steady Qualitative test figure.
Fig. 7 B is Ni3S2The ladder time-measuring electric potential test chart of@Ni-Fe LDH analysis oxygen electro catalytic electrode.
Fig. 8 is Ni3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode, comparative sample 1, IrO2The Tafel slope figure of/C electrode.
Fig. 9 is the SEM figure of comparative sample 2.
Figure 10 is the SEM figure of comparative sample 3.
Figure 11 A, Figure 11 B are the SEM figures of comparative sample 4.
Figure 12 is the SEM figure of comparative sample 5.
Figure 13 is the XRD diagram of comparative sample 5.
Figure 14 A, Figure 14 B are constant current gas evolution figure under 4 same current density of comparative sample 1 and comparative sample respectively.
Specific embodiment
Below with reference to embodiment and attached drawing, specific implementation of the invention is described further, but embodiment party of the invention Formula is without being limited thereto.
Embodiment 1
(1) pretreatment of matrix: pure nickel piece is cut to the rectangle of 3.5cm0.5cm, the 1cm of top half is as folder Part is held, the 2.5cm of lower half portion immerses in electrolyte as actual use part and carries out anodized.After cutting Matrix be put into ultrasonic vibration 20 minutes in acetone, place into dehydrated alcohol ultrasonic vibration 20 minutes and carry out, then spend from Sub- water cleans up.
(2) anodic oxidation of matrix: anodic oxidation electrolyte is prepared by solvent of deionized water, electrolyte composition is 1wt% ammonium fluoride, 80wt% phosphoric acid, remaining is deionized water.The actual use part of step (1) pretreated matrix is soaked Enter in electrolyte, retained part is connect with anode electrode.Anodic oxidation device is SP-150 electrochemical workstation, using three electrodes System, matrix are used as working electrode, platinum electrode to electrode, and saturated calomel electrode is as reference electrode.With the speed of 10mV/s Rate boosts to 3.5V by open circuit potential, is kept for constant pressure 10 minutes, 25 DEG C of electrolyte temperature in 3.5V.
(3) sample is removed after the completion of anodic oxidation, is rinsed well and is dried up using deionized water.
(4) vulcanization hydro-thermal is carried out to the sample after anodic oxidation, with deionized water formulating vulcanization hydrothermal solution, solution composition For 0.05mol/L vulcanized sodium, 0.1mol/L ammonium fluoride, the ethyl alcohol of 10mol/L, remaining is deionized water；By sample with prepare Vulcanization hydrothermal solution be added hydrothermal reaction kettle in, hydrothermal reaction kettle volume be 25mL, be added solution 10mL, plot ratio 40%.
(5) by hydrothermal reaction kettle it is closed after be put into chamber type electric resistance furnace and heat, hydrothermal temperature is 120 DEG C, when hydro-thermal Between be 12 hours, reaction kettle is taken out from resistance furnace after hydro-thermal and is air-cooled to room temperature, open reaction kettle taking-up sample, spend from Sub- water is rinsed well and is dried up, and nano bar-shape Ni is obtained3S2Film layer.
(6) to the nano bar-shape Ni of step (5) preparation3S2Film layer carries out mixing molten iron heat, mixes molten iron heat with deionized water preparation Solution, solution composition are 1mmol/L ferric trichloride, and 0.5mol/L ammonium fluoride, 0.2mol/L neopelex, remaining is Deionized water.Sample and prepared solution are added in hydrothermal reaction kettle, hydrothermal reaction kettle volume is 25mL, and solution is added 10mL, plot ratio 40%.
(7) by hydrothermal reaction kettle it is closed after be put into chamber type electric resistance furnace and heat, hydrothermal temperature is 120 DEG C, when hydro-thermal Between be 6 hours, reaction kettle is taken out from resistance furnace after hydro-thermal and is air-cooled to room temperature, open reaction kettle taking-up sample, use deionization Water is rinsed well and is dried up, and Ni is obtained3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode.
Using three-electrode system to Ni3S2The analysis oxygen catalytic performance of@Ni-Fe LDH analysis oxygen electro catalytic electrode is tested, Ni3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode as working electrode, and platinum electrode is used as to electrode, and mercuric oxide electrode is as reference Electrode.Electrolyte used in testing is the potassium hydroxide solution of 1mol/L, to Ni3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode Cyclic voltammetry or constant current test are carried out, with analysis oxygen current density size achieved under a certain current potential or reaches a certain analysis oxygen The analysis oxygen electrocatalysis characteristic of the expression electrode of overpotential size needed for current density.
For the performance for better illustrating electrode prepared by the present invention, the present embodiment prepares comparative sample 1~5, is tested knot Fruit and Ni of the invention3S2@Ni-Fe LDH analysis oxygen electro catalytic electrode is compared, wherein the implementation method of each comparative sample preparation is such as Under:
Comparative sample 1
(1) pretreatment of matrix, it is identical as embodiment 1 step (1).
(2) anodic oxidation of matrix, it is identical as embodiment 1 step (2).
(3) sample is removed after the completion of anodic oxidation, is rinsed well and is dried up using deionized water.
(4) vulcanization hydro-thermal is carried out to the sample after anodic oxidation, with deionized water formulating vulcanization hydrothermal solution, solution composition For 0.05mol/L vulcanized sodium, 0.1mol/L ammonium fluoride, 10mol/L ethyl alcohol, remaining is deionized water.By sample with it is prepared Solution is added in hydrothermal reaction kettle, and hydrothermal reaction kettle volume is 25mL, and solution 10mL, plot ratio 40% is added.
(5) by hydrothermal reaction kettle it is closed after be put into chamber type electric resistance furnace and heat, hydrothermal temperature is 120 DEG C, when hydro-thermal Between be 12 hours, sample is taken out after hydro-thermal, is rinsed well and is dried up with deionized water, obtains nano bar-shape Ni3S2Film layer.
Comparative sample 2
(1) pretreatment of matrix, it is identical as embodiment 1 step (1).
(2) anodic oxidation of matrix, it is identical as embodiment 1 step (2).
(3) sample is removed after the completion of anodic oxidation, is rinsed well and is dried up using deionized water.
(4) vulcanization hydro-thermal is carried out to the sample after anodic oxidation, with deionized water formulating vulcanization hydrothermal solution, solution composition For 0.05mol/L vulcanized sodium, 0.1mol/L ammonium fluoride, remaining is deionized water.Hydro-thermal is added in sample and prepared solution In reaction kettle, hydrothermal reaction kettle volume is 25mL, and solution 10mL, plot ratio 40% is added.
(5) by hydrothermal reaction kettle it is closed after be put into chamber type electric resistance furnace and heat, hydrothermal temperature is 120 DEG C, when hydro-thermal Between be 12 hours, sample is taken out after hydro-thermal, is rinsed well and is dried up with deionized water, obtains nano bar-shape Ni3S2Film layer.
Comparative sample 3
(1) pretreatment of matrix, it is identical as embodiment 1 step (1).
(2) vulcanization hydro-thermal is directly carried out to pretreated matrix, with deionized water formulating vulcanization hydrothermal solution, solution at Be divided into 0.05mol/L vulcanized sodium, 0.1mol/L ammonium fluoride, 10mol/L ethyl alcohol, remaining is deionized water, by sample with prepare Solution be added hydrothermal reaction kettle in, hydrothermal reaction kettle volume be 25mL, be added solution 10mL, plot ratio 40%.
(3) by hydrothermal reaction kettle it is closed after be put into chamber type electric resistance furnace and heat, hydrothermal temperature is 120 DEG C, when hydro-thermal Between be 12 hours, sample is taken out after hydro-thermal, is rinsed well and is dried up with deionized water.
The comparative sample directly carries out vulcanization hydro-thermal without anodized, forms the Ni of plane microstructure3S2Film layer (see Figure 10).
Comparative sample 4
(1) pretreatment of matrix, it is identical as embodiment 1 step (1).
(2) vulcanization hydro-thermal is carried out to pretreated matrix, with deionized water formulating vulcanization hydrothermal solution, solution composition is 0.05mol/L vulcanized sodium, 0.35mol/L nickel nitrate, 10mol/L ethyl alcohol, remaining is deionized water, by sample with it is prepared molten Liquid is added in hydrothermal reaction kettle, and hydrothermal reaction kettle volume is 25mL, and solution 10mL, plot ratio 40% is added.
(3) by hydrothermal reaction kettle it is closed after be put into chamber type electric resistance furnace and heat, hydrothermal temperature is 120 DEG C, when hydro-thermal Between be 12 hours, sample is taken out after hydro-thermal, is rinsed well and is dried up with deionized water.
Comparative sample 5
(1) pretreatment of matrix, it is identical as embodiment 1 step (1).
(2) pretreated matrix in step (1) is carried out mixing molten iron heat, molten iron hot solution is mixed with deionized water preparation, Solution composition be 1mmol/L ferric trichloride, 0.5mol/L ammonium fluoride, 0.2mol/L neopelex, remaining for go from Sample and prepared solution are added in hydrothermal reaction kettle water, and hydrothermal reaction kettle volume is 25mL, and solution 10mL is added, Plot ratio 40%.
(3) by hydrothermal reaction kettle it is closed after be put into chamber type electric resistance furnace and heat, hydrothermal temperature is 120 DEG C, when hydro-thermal Between be 6 hours, sample is taken out after hydro-thermal, is rinsed well and is dried up with deionized water, obtains Ni Ni-Fe LDH film layer.
The comparative sample Ni substrate directly carries out mixing molten iron heat treatment, on Ni substrate surface without anodic oxidation, vulcanizing treatment Layer of Ni-Fe LDH film is obtained, microscopic appearance is to be laid on matrix (see Figure 12, Figure 13).
To Ni manufactured in the present embodiment3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode and the surface topography of comparative sample 1 carries out table Sign, SEM test result is as shown in Figure 1A, Figure 1B, and TEM test result is as shown in Fig. 2A, Fig. 2 B, as can be observed from Figure, By anodic oxidation and vulcanization hydro-thermal process, obtained film layer is nano bar-shape structure, and nanometer rods are vertical with base, mutually flat Row, surface are smooth；Using molten iron heat treatment is mixed, there is the film of flaky nanometer structure, film in nano bar-shape body structure surface With nanometer rods Parallel Growth.
To Ni manufactured in the present embodiment3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode and the institutional framework of comparative sample 1 carries out table Sign, XRD test result is as shown in Fig. 3 A, Fig. 3 B, the as can be seen from the figure characteristic peak and Ni of matrix Ni3S2Characteristic peak.By In the parallel Ni of Ni-Fe LDH3S2Nanorod growth, Ni-Fe LDH characteristic peak does not occur in XRD.
To Ni manufactured in the present embodiment3S2@Ni-Fe LDH analysis oxygen electro catalytic electrode and the ingredient of comparative sample 1 are characterized, Its XPS test result is as shown in Fig. 4 A, Fig. 4 B.As can be seen from Figure 4A, Ni3S2@Ni-Fe LDH analyse oxygen electro catalytic electrode with Ni3S2There is the characteristic peak of Ni in the XPS test of nanometer rods, wherein Ni3S2Characteristic peak in the test chart of electrode intensity become Weak, the characteristic peak position of the Ni high 0.4eV after mixing molten iron heat illustrates that the average valence of Ni is hankered increasing mixing molten iron.From Fig. 4 B It can be seen that Ni3S2There is characteristic peak in 712.1eV and 725eV in@Ni-Fe LDH electrode, this is Fe3+Characteristic peak, show Fe3+It enters in LDH film.
To Ni manufactured in the present embodiment3S2The ingredient of@Ni-Fe LDH analysis oxygen electro catalytic electrode is characterized, Raman spectrum Test results are shown in figure 5, as can be seen from the figure removes Ni3S2Characteristic peak outside, in 495cm‐1And 575cm‐1Occur two Characteristic peak is Fe respectively3+/Ni2+‐O‐Ni2+And Fe3+‐O‐Fe3+Characteristic peak, show the presence of Ni-Fe LDH.
Fig. 6 is Ni manufactured in the present embodiment3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode and comparative sample 1, IrO2/ C electrode with And cyclic voltammetry curve of the pure nickel piece in the KOH solution of 1mol/L.It can be seen from the figure that matrix pure nickel piece is to electrolysis The catalytic capability of water oxygen evolution reaction is very weak, IrO2/ C electrode, Ni3S2Nanometer rods, Ni3S2@Ni-Fe LDH analyse oxygen electro-catalysis electricity Extremely show higher catalytic performance, but Ni3S2The catalytic performance of@Ni-Fe LDH analysis oxygen electro catalytic electrode is substantially better than other Sample, analysis oxygen take-off potential are 1.42V vs RHE, and the analysis oxygen current density under 300mV overpotential is 90mA/cm2, reach 10mA/cm2Overpotential needed for current density is 245mV.
Fig. 7 A is Ni manufactured in the present embodiment3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode and IrO2/ C electrode is in 1mol/L KOH solution in analyse oxidative stability test result for a long time, with 10mA/cm2Current density carries out constant current reaction, Ni3S2@Ni‐ Fe LDH analysis oxygen electro catalytic electrode overpotential for oxygen evolution in initial 2.5h is greatly lowered, this is Ni based compound in constant current item The process activated under part only rises 5mV, IrO by the reaction oxygen evolution potential of constant current in 40 hours after activation2/ C electrode did not activate Journey, oxygen evolution potential rises 30mV after the constant current of 10h reaction.
Fig. 7 B is that the present embodiment prepares Ni3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode ladder in the KOH solution of 1mol/L Time-measuring electric potential test result, initial current density 5mA/cm2, each step difference 5mA/cm2And 3min is kept, it increases to 50mA/cm2Every single order reduces 5mA/cm afterwards2, and 3min is kept, it is eventually returned to 5mA/cm2.It can be seen from the figure that every single order meter When potential region OER current potential it is all sufficiently stable, and current density increase with reduce during, with analysis oxygen electricity when current density Position is almost the same.These results suggest that Ni3S2@Ni-Fe LDH, which analyses oxygen electro catalytic electrode, has good mass transfer ability, electricity Rapidly, it is fast that gas diffusion escapes speed for son transfer.
Fig. 8 is Ni manufactured in the present embodiment3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode, comparative sample 1 and IrO2/ C electrode Tafel slope figure.It can be seen from the figure that Ni3S2The Tafel slope of@Ni-Fe LDH analysis oxygen electro catalytic electrode is significantly less than Ni3S2Nanometer rods and IrO2/ C electrode, show Ni3S2@Ni-Fe LDH analyses the analysis oxygen current density of oxygen electro catalytic electrode with excessively electric Position rises and rises faster.
Fig. 9 is the SEM figure of comparative sample 2, it can be seen from the figure that the sample after anodic oxidation, in vulcanization water-heat process In, when ethyl alcohol is not added for hydrothermal solution, the film of a layer plane structure is covered in nanometer rods, this coating is unfavorable for increasing electricity Solve the contact area of liquid and nanorod structure.
Figure 10 is the SEM figure of comparative sample 3, it can be seen from the figure that the nickel sheet without anodic oxidation directly carries out sulphurous water Heat obtains the film layer of plane microstructure, and the contact area of the microscopic appearance electrolyte and electrode is much smaller than nano bar-shape pattern.
Figure 11 A, Figure 11 B are the SEM figures of comparative sample 4, it can be seen from the figure that the nickel sheet without anodic oxidation directly carries out Hydro-thermal vulcanization, is added nickel ion in the solution, and the film layer of nano whiskers structure, but nanoneedle and base's out of plumb, phase can be obtained Mutually staggeredly, and there are ribbon, this pattern is unfavorable for the evolution of the gas generated in electrolysis water reaction.
Figure 12 is the SEM figure of comparative sample 5, it can be seen from the figure that directly carry out mixing the nickel sheet of molten iron heat after pretreatment, Surface forms the film of layer plane distribution.
Figure 13 is the XRD diagram of comparative sample 5, it can be seen from the figure that occurring in addition to the characteristic peak of matrix Ni in three angles The characteristic peak of Ni-Fe LDH, shows in the molten iron of mixing of the present embodiment to hanker that Ni-Fe LDH can be formed.
Figure 14 A, Figure 14 B respectively indicate comparative sample 1 and comparative sample 4 in 10mA/cm2Gas evolution situation under current density, It can be seen from the figure that nickel sheet vulcanizes the Ni of hydro-thermal process through anodic oxidation3S2Nano bar-shape film layer is in electrolysis elutriation oxygen catalysis The bubble being precipitated in reaction is smaller, and nickel sheet is adding the film layer that vulcanization hydro-thermal process obtains in nickel source solution being electrolysed elutriation oxygen outside The bubble being precipitated in reaction out is larger.This shows Ni of the nickel sheet through anodic oxidation, vulcanization hydro-thermal process3S2Nano bar-shape film layer exists It is more advantageous to the evolution of gas in electrolysis elutriation oxygen catalysis reaction, to promote continuing for reaction.
Embodiment 2
(1) pretreatment of matrix, it is identical as embodiment 1 step (1).
(2) anodic oxidation of matrix, in addition to electrolyte composition is 2wt% ammonium fluoride, 85wt% phosphoric acid, remaining is deionization Outside water, other conditions are identical as embodiment 1 step (2).
(3) sample is removed after the completion of anodic oxidation, is rinsed well and is dried up using deionized water.
(4) vulcanization hydro-thermal is carried out to the sample after anodic oxidation, hydrothermal solution is vulcanized with deionized water, solution composition is 0.02mol/L vulcanized sodium, 0.1mol/L ammonium fluoride, 5mol/L ethyl alcohol, remaining is deionized water, by sample and prepared solution It is added in hydrothermal reaction kettle, hydrothermal reaction kettle volume is 25mL, and solution 10mL, plot ratio 40% is added.
(5) by hydrothermal reaction kettle it is closed after be put into chamber type electric resistance furnace in heat, hydrothermal temperature be 140 DEG C, hydro-thermal Time is 6 hours, takes out sample after hydro-thermal, is rinsed well and dried up with deionized water, obtains nano bar-shape Ni3S2Film layer.
(6) to the nano bar-shape Ni of step (5) preparation3S2Film layer carries out mixing molten iron heat, mixes molten iron heat with deionized water preparation Solution, solution composition are 2mmol/L ferric trichloride, and 1mol/L ammonium fluoride, 0.5mol/L neopelex, remaining is to go Ionized water.Sample and prepared solution are added in hydrothermal reaction kettle, hydrothermal reaction kettle volume is 25mL, and solution is added 10mL, plot ratio 40%.
(7) by hydrothermal reaction kettle it is closed after be put into chamber type electric resistance furnace in heat, hydrothermal temperature be 110 DEG C, hydro-thermal Time is 8 hours, takes out sample after hydro-thermal, is rinsed well and dried up with deionized water, obtains Ni3S2@Ni-Fe LDH analyses oxygen Electro catalytic electrode.
Analysis oxygen prepared by surface topography, institutional framework and embodiment 1 through analysis oxygen electro catalytic electrode manufactured in the present embodiment Electro catalytic electrode is similar, is that Ni-Fe LDH nano thin-film is grown on Ni3S2On nanometer rods.Analysis oxygen take-off potential is 1.422V Vs RHE, the analysis oxygen current density under 300mV overpotential are 87mA/cm2, reach 10mA/cm2It is excessively electric needed for current density Position is 247mV, in 10mA/cm2Only rise 5.6mV through 40 hours constant current oxygen evolution reaction oxygen evolution potentials under current density.
Embodiment 3
(1) pretreatment of matrix, it is identical as embodiment 1 step (1).
(2) anodic oxidation of matrix: anodic oxidation electrolyte is prepared by solvent of deionized water, electrolyte composition is 0.5wt% ammonium fluoride, 75wt% phosphoric acid, remaining is deionized water.By the actual use part of step (1) pretreated matrix It immerses in electrolyte, retained part is connect with anode electrode.Anodic oxidation device is SP-150 electrochemical workstation, using three electricity Polar body system, matrix are used as working electrode, platinum electrode to electrode, and saturated calomel electrode is as reference electrode.With 10mV/s's Rate boosts to 5V by open circuit potential, is kept for constant pressure 5 minutes, 25 DEG C of electrolyte temperature in 5V.
(3) sample is removed after the completion of anodic oxidation, is rinsed well and is dried up using deionized water.
(4) vulcanization hydro-thermal is carried out to the sample after anodic oxidation, with deionized water formulating vulcanization hydrothermal solution, solution composition For 0.03mol/L vulcanized sodium, 0.15mol/L ammonium fluoride, the ethyl alcohol of 12mol/L, remaining is deionized water；By sample and prepare Good vulcanization hydrothermal solution is added in hydrothermal reaction kettle, and hydrothermal reaction kettle volume is 25mL, and solution 10mL, plot ratio is added 40%.
(5) by hydrothermal reaction kettle it is closed after be put into chamber type electric resistance furnace and heat, hydrothermal temperature is 100 DEG C, when hydro-thermal Between be 9 hours, reaction kettle is taken out from resistance furnace after hydro-thermal and is air-cooled to room temperature, open reaction kettle taking-up sample, use deionization Water is rinsed well and is dried up, and nano bar-shape Ni is obtained3S2Film layer.
(6) to the nano bar-shape Ni of step (5) preparation3S2Film layer carries out mixing molten iron heat, mixes molten iron heat with deionized water preparation Solution, solution composition be 0.5mmol/L ferric trichloride, 0.1mol/L ammonium fluoride, 0.1mol/L neopelex, remaining For deionized water.Sample and prepared solution are added in hydrothermal reaction kettle, hydrothermal reaction kettle volume is 25mL, and solution is added 10mL, plot ratio 40%.
(7) by hydrothermal reaction kettle it is closed after be put into chamber type electric resistance furnace and heat, hydrothermal temperature is 130 DEG C, when hydro-thermal Between be 3 hours, reaction kettle is taken out from resistance furnace after hydro-thermal and is air-cooled to room temperature, open reaction kettle taking-up sample, use deionization Water is rinsed well and is dried up, and Ni is obtained3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode.
The analysis oxygen electricity prepared through analysis oxygen electro catalytic electrode surface topography, institutional framework and embodiment 1 manufactured in the present embodiment Catalysis electrode is similar, is that Ni-Fe LDH nano thin-film is grown on Ni3S2On nanometer rods.Analysis oxygen take-off potential is 1.422V Vs RHE, the analysis oxygen current density under 300mV overpotential are 85mA/cm2, reach 10mA/cm2It is excessively electric needed for current density Position is 249mV, in 10mA/cm2Only rise 6.1mV through 40 hours constant current oxygen evolution reaction oxygen evolution potentials under current density.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not limited to the specific embodiments Concrete mode, it is other it is any without departing from the spirit and principles of the present invention made by change, substitution, combination, simplify, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (8)

1. a kind of Ni3S2The preparation method of@Ni-Fe LDH analysis oxygen electro catalytic electrode, which comprises the following steps:
(1) Ni substrate is immersed in electrolyte, carries out constant pressure anodized using three electrodes；
(2) gained sample after step (1) processing and vulcanization hydrothermal solution are added in hydrothermal reaction kettle at 100 DEG C -140 DEG C Vulcanization hydro-thermal process is carried out, is rinsed with water after processing completely, drying obtains nano bar-shape Ni3S2Film layer；
(3) by nano bar-shape Ni obtained by step (2)3S2Film layer and mix molten iron hot solution be added hydrothermal reaction kettle in carry out mixing molten iron Heat treatment, is rinsed with water completely after processing, and drying obtains Ni3S2@Ni-Fe LDH analyses oxygen electro catalytic electrode；
Electrolyte used in step (1) described anodized contains the ammonium fluoride of 0.5-2wt% and the phosphorus of 75-85wt% Acid；
Contain the vulcanized sodium of 0.02-0.05mol/L, the fluorination of 0.1-0.2mol/L in step (2) the vulcanization hydrothermal solution The ethyl alcohol of ammonium and 5-12mol/L.
2. preparation method according to claim 1, which is characterized in that step (1) anodized uses platinum electricity Pole is used as to electrode, and saturated calomel electrode is as reference electrode.
3. preparation method according to claim 1, which is characterized in that the constant pressure electricity of step (1) described anodized Position is 3-5V, and the temperature of electrolyte is 15-35 DEG C, and the time of anodic oxidation is 5-10 minutes.
4. preparation method according to claim 1, which is characterized in that the filling rate of step (2) described hydrothermal reaction kettle is 40%—50%；The time of the vulcanization hydro-thermal is 6-12 hours.
5. preparation method according to claim 1, which is characterized in that the filling rate of step (3) described hydrothermal reaction kettle is 40%—50%；The temperature for mixing molten iron heat is 110 DEG C-130 DEG C, and the time is 3-8 hours.
6. preparation method according to claim 1, which is characterized in that step (3) described mix is contained in molten iron hot solution The ferric trichloride of 0.5-2mmol/L, the ammonium fluoride of 0.1-1mol/L and the detergent alkylate sulphur of 0.1mol/L-0.5mol/L Sour sodium.
7. a kind of Ni being prepared by the described in any item preparation methods of claim 1-63S2@Ni-Fe LDH analysis oxygen electricity is urged Polarizing electrode.
8. a kind of Ni as claimed in claim 73S2@Ni-Fe LDH analyses oxygen electro catalytic electrode as anode of electrolytic water oxygen evolution reaction Catalysis electrode application.
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