CN107904614A - A kind of Ni3S2@Ni Fe LDH analysis oxygen electro catalytic electrodes and preparation method and application - Google Patents

A kind of Ni3S2@Ni Fe LDH analysis oxygen electro catalytic electrodes and preparation method and application Download PDF

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CN107904614A
CN107904614A CN201710967077.XA CN201710967077A CN107904614A CN 107904614 A CN107904614 A CN 107904614A CN 201710967077 A CN201710967077 A CN 201710967077A CN 107904614 A CN107904614 A CN 107904614A
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ldh
preparation
electrode
oxygen
reaction kettle
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CN107904614B (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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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 analysis oxygen electro catalytic electrodes and preparation method and application, belong to electrolysis elutriation oxygen catalytic field.The preparation method comprises the following steps：The pretreatment of Ni substrate, 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 vulcanizing hydro-thermal3S2Film layer；Film layer after vulcanizing treatment is carried out to mix molten iron heat, obtains Ni3S2@Ni Fe LDH analyse oxygen electro catalytic electrode.The method of the present invention is novel, and simple operation is of low cost, is adapted to industrial production, the Ni of preparation3S2@Ni Fe LDH electrode materials are used for electrolysis water oxygen evolution reaction, and catalytic activity is high, and stability is good, available for industrialization electrolysis water production.

Description

A kind of Ni3S2@Ni-Fe LDH analysis oxygen electro catalytic electrodes and preparation method and application
Technical field
The present invention relates to electro-catalysis and electrolysis water field, more particularly to a kind of Ni3S2@Ni-Fe LDH analyse oxygen electro catalytic electrode And preparation method and application.
Background technology
Since fossil fuel faces exhaustion and there are problem of environmental pollution, the novel energy for substituting conventional fossil fuel is developed It is very necessary.The novel energy being widely studied at present has solar energy, wind energy, nuclear energy, Hydrogen Energy, and wherein solar energy and wind energy is by day Gas influences greatly, and source is unstable, and nuclear energy has hidden danger caused by leakage.It is completely pollution-free to environment and Hydrogen Energy is easy to use, energy Metric density is high, and utilization ratio is high, becomes the hot spot of novel energy area research.
In current hydrogen preparation technique, water electrolysis hydrogen production is that a kind of application is relatively wide, the method for technology maturation.Industry at present On the electrolyzed alkaline water method voltage that uses be far above theoretical voltage, at least 25% power consumption is used to overcome overpotential, its The excessive overpotential of Anodic oxygen evolution reaction is principal element, therefore the oxygen-separating catalyst developed efficiently, stable 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 and urge in the alkaline electrolyte Change performance, and derive from a wealth of sources, is of low 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 has decisive action with electronic structure to catalytic activity.Material Expect that making Nano surface with Fe element dopings has been demonstrated that the catalytic active of nickel base electrode can be effectively improved, Ni-Fe LDH are recognized To be most potential Ni-based analysis oxygen catalysis material.Substantial amounts of research, which efforts be made so as to be prepared with different methods, has various nanometers The Ni-FeLDH of pattern, such as electrodeposition process, chemical deposition, template, sol-gal process etc..The above method achieves certain Achievement, but the nickel-base catalyst of more counting methods preparation and the combination power of matrix is not high, in prolonged oxygen evolution reaction easily Come off from matrix, influence the efficiency of electrolysis water；On the other hand, the Ni-Fe LDH of nanosizing are easy to reunite in the synthesis process, It is unfavorable for exposing more active sites.
The content of the invention
For overcome the deficiencies in the prior art, the present invention provides a kind of Ni with core@shell structures3S2@Ni‐Fe LDH Oxygen electro catalytic electrode and preparation method and application is analysed, i.e., by anodizing and hydro-thermal method, prepares composite construction Ni3S2@Ni-Fe LDH materials, analyse it oxygen catalytic activity, analyse 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 present invention is achieved through the following technical solutions.
A kind of Ni3S2@Ni-Fe LDH analyse the preparation method of oxygen electro catalytic electrode, comprise the following steps：
(1) Ni substrate is immersed in electrolyte, constant pressure anodized is carried out using three electrodes；
(2) gained sample after step (1) processing is added in hydrothermal reaction kettle with vulcanization hydrothermal solution and carries out vulcanization hydro-thermal Processing, is rinsed well after processing with water, is dried up, is obtained nano bar-shape Ni3S2Film layer；
(3) by nano bar-shape Ni obtained by step (2)3S2Film layer is mixed with mixing molten iron hot solution and adding in hydrothermal reaction kettle Molten iron is heat-treated, and is rinsed well after processing with water, is dried up, is obtained Ni3S2@Ni-Fe LDH analyse 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 to be used 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, when the time is 6~12 small.
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 ethanol of 5~12mol/L.
Preferably, the filling rate of step (3) described hydrothermal reaction kettle is 40%~50%；It is described mix molten iron heat temperature be 110 DEG C~120 DEG C, when the time is 3~8 small.
Preferably, step (3) is described mixes the ferric trichloride containing 0.5~2mmol/L, 0.1~1mol/ in molten iron hot solution 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 analyse oxygen electro catalytic electrode.
A kind of above-described Ni3S2@Ni-Fe LDH analyse oxygen electro catalytic electrode urging as anode of electrolytic water oxygen evolution reaction Polarizing electrode.
Compared with existing analysis oxygen catalytic electrode material, the present invention has the following advantages：
(1) Ni of the invention3S2The analysis oxygen catalytic performance of@Ni-Fe LDH analysis oxygen electro catalytic electrodes 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 electrodes are with good stability, analysing for a long time In the test of oxygen catalytic reaction, through 10mA/cm2When current density constant current 40 is small, overpotential is held essentially constant, and has 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 combination power and electric conductivity between matrix, can directly be used in the case where not adding conductive agent or bonding agent, both The preparation process of electrode is simplified, turn avoid the problem of catalytic activity caused 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 speed； Based on the bigger serface of nano bar-shape structure, Ni-Fe LDH catalyst can be uniformly distributed in Ni3S2On nanometer rods, solve The problem of Ni-FeLDH is easy to reunite, while has increased considerably the specific surface area of catalyst, the more avtive spots of exposure with Electrolyte solution contacts.
(5) raw material sources of the invention are extensive, and of low cost, technique is simple, simple operation, the electrode analysis oxygen catalysis of preparation Performance is high, and stability is strong, available for electrolysis elutriation oxygen catalytic field.
Brief description of the drawings
Figure 1A is Ni3S2The SEM figures of@Ni-Fe LDH analysis oxygen electro catalytic electrodes.
Figure 1B is the SEM figures of comparative sample 1.
Fig. 2A is Ni3S2The TEM figures of@Ni-Fe LDH analysis oxygen electro catalytic electrodes.
Fig. 2 B are the TEM figures of comparative sample 1.
Fig. 3 A are Ni3S2@Ni-Fe LDH analyse the XRD diagram of oxygen electro catalytic electrode.
Fig. 3 B are the XRD diagram of comparative sample 1.
Fig. 4 A are Ni3S2@Ni-Fe LDH analyse oxygen electro catalytic electrode and the nickel element XPS of comparative sample 1 schemes, and Fig. 4 B are Ni3S2
The ferro element XPS figures of@Ni-Fe LDH analysis oxygen electro catalytic electrodes.
Fig. 5 is Ni3S2@Ni-Fe LDH analyse the Raman spectrogram of oxygen electro catalytic electrode.
Fig. 6 is Ni3S2@Ni-Fe LDH analyse oxygen electro catalytic electrode and comparative sample 1, IrO2The electrolysis of/C electrode, pure nickel piece Elutriation oxygen catalytic performance test CV schemes.
Fig. 7 A are Ni3S2@Ni-Fe LDH analyse oxygen electro catalytic electrode and IrO2The electrolysis elutriation oxygen catalysis of/C electrodes is long-term steady Qualitative test figure.
Fig. 7 B are Ni3S2@Ni-Fe LDH analyse the ladder time-measuring electric potential test chart of oxygen electro catalytic electrode.
Fig. 8 is Ni3S2@Ni-Fe LDH analysis oxygen electro catalytic electrode, comparative sample 1, IrO2The Tafel slope figures of/C electrodes.
Fig. 9 is the SEM figures of comparative sample 2.
Figure 10 is the SEM figures of comparative sample 3.
Figure 11 A, Figure 11 B are the SEM figures of comparative sample 4.
Figure 12 is the SEM figures 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.
Embodiment
With reference to embodiment and attached drawing, the specific implementation to the present invention is described further, but the embodiment party of the present invention Formula not limited to this.
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 the latter half 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 absolute ethyl alcohol ultrasonic vibration and carry out for 20 minutes, then spend from Sub- water cleans up.
(2) anodic oxidation of matrix：Anodic oxidation electrolyte is prepared by solvent of deionized water, bath composition is 1wt% ammonium fluorides, 80wt% phosphoric acid, remaining is deionized water.The actual use part of step (1) pretreated matrix is soaked Enter in electrolyte, retained part is connected with anode electrode.Anodic oxidation device is SP-150 electrochemical workstations, using three electrodes System, matrix are used as to electrode as working electrode, platinum electrode, and saturated calomel electrode is as reference electrode.With the speed of 10mV/s Rate boosts to 3.5V by open circuit potential, keeps constant pressure 10 minutes in 3.5V, 25 DEG C of electrolyte temperature.
(3) sample is removed after the completion of anodic oxidation, it is clean using deionized water rinsing and dry up.
(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 fluorides, the ethanol of 10mol/L, remaining is deionized water；By sample with preparing Vulcanization hydrothermal solution add hydrothermal reaction kettle in, hydrothermal reaction kettle volume be 25mL, addition solution 10mL, plot ratio 40%.
(5) by hydrothermal reaction kettle it is closed after be put into chamber type electric resistance furnace and heated, hydrothermal temperature is 120 DEG C, during hydro-thermal Between for 12 it is small when, reaction kettle is taken out from resistance furnace after hydro-thermal and is air-cooled to room temperature, opened reaction kettle taking-up sample, use deionization Water is rinsed well and dried up, and obtains nano bar-shape Ni3S2Film layer.
(6) the nano bar-shape Ni prepared to step (5)3S2Film layer carries out mixing molten iron heat, is prepared with deionized water and mixes molten iron heat Solution, solution composition are 1mmol/L ferric trichlorides, and 0.5mol/L ammonium fluorides, 0.2mol/L neopelexes, remaining is Deionized water.Sample and prepared solution are added in hydrothermal reaction kettle, hydrothermal reaction kettle volume is 25mL, adds solution 10mL, plot ratio 40%.
(7) by hydrothermal reaction kettle it is closed after be put into chamber type electric resistance furnace and heated, hydrothermal temperature is 120 DEG C, during hydro-thermal Between for 6 it is small when, reaction kettle is taken out from resistance furnace after hydro-thermal and is air-cooled to room temperature, opened reaction kettle taking-up sample, use deionization Water is rinsed well and dried up, and obtains Ni3S2@Ni-Fe LDH analyse oxygen electro catalytic electrode.
Using three-electrode system to Ni3S2The analysis oxygen catalytic performance of@Ni-Fe LDH analysis oxygen electro catalytic electrodes is tested, Ni3S2@Ni-Fe LDH analyse oxygen electro catalytic electrode and are used as working electrode, platinum electrode to electrode, and mercuric oxide electrode is as reference Electrode.Electrolyte used in test is the potassium hydroxide solution of 1mol/L, to Ni3S2@Ni-Fe LDH analyse oxygen electro catalytic electrode Cyclic voltammetry or constant current test are carried out, with the analysis oxygen current density size reached under a certain current potential or reaches a certain analysis oxygen Overpotential size needed for current density represents the analysis oxygen electrocatalysis characteristic of electrode.
To better illustrate the performance of electrode prepared by the present invention, the present embodiment prepares comparative sample 1~5, is tested knot Fruit and the Ni of the present invention3S2@Ni-Fe LDH analysis oxygen electro catalytic electrodes are compared, wherein implementation prepared by each comparative sample is such as Under：
Comparative sample 1
(1) pretreatment of matrix, it is identical with 1 step of embodiment (1).
(2) anodic oxidation of matrix, it is identical with 1 step of embodiment (2).
(3) sample is removed after the completion of anodic oxidation, it is clean using deionized water rinsing and dry up.
(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 fluorides, 10mol/L ethanol, remaining is deionized water.By sample with it is prepared Solution is added in hydrothermal reaction kettle, and hydrothermal reaction kettle volume is 25mL, adds solution 10mL, plot ratio 40%.
(5) by hydrothermal reaction kettle it is closed after be put into chamber type electric resistance furnace and heated, hydrothermal temperature is 120 DEG C, during hydro-thermal Between for 12 it is small when, sample is taken out after hydro-thermal, is rinsed well and dried up with deionized water, obtain nano bar-shape Ni3S2Film layer.
Comparative sample 2
(1) pretreatment of matrix, it is identical with 1 step of embodiment (1).
(2) anodic oxidation of matrix, it is identical with 1 step of embodiment (2).
(3) sample is removed after the completion of anodic oxidation, it is clean using deionized water rinsing and dry up.
(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 fluorides, remaining is deionized water.Sample and prepared solution are added into hydro-thermal In reaction kettle, hydrothermal reaction kettle volume is 25mL, adds solution 10mL, plot ratio 40%.
(5) by hydrothermal reaction kettle it is closed after be put into chamber type electric resistance furnace and heated, hydrothermal temperature is 120 DEG C, during hydro-thermal Between for 12 it is small when, sample is taken out after hydro-thermal, is rinsed well and dried up with deionized water, obtain nano bar-shape Ni3S2Film layer.
Comparative sample 3
(1) pretreatment of matrix, it is identical with 1 step of embodiment (1).
(2) vulcanization hydro-thermal is directly carried out to pretreated matrix, with deionized water formulating vulcanization hydrothermal solution, solution into It is divided into 0.05mol/L vulcanized sodium, 0.1mol/L ammonium fluorides, 10mol/L ethanol, remaining is deionized water, by sample with preparing Solution add hydrothermal reaction kettle in, hydrothermal reaction kettle volume be 25mL, addition solution 10mL, plot ratio 40%.
(3) by hydrothermal reaction kettle it is closed after be put into chamber type electric resistance furnace and heated, hydrothermal temperature is 120 DEG C, during hydro-thermal Between for 12 it is small when, sample is taken out after hydro-thermal, is rinsed well and 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 with 1 step of embodiment (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 nitrates, 10mol/L ethanol, 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, adds solution 10mL, plot ratio 40%.
(3) by hydrothermal reaction kettle it is closed after be put into chamber type electric resistance furnace and heated, hydrothermal temperature is 120 DEG C, during hydro-thermal Between for 12 it is small when, sample is taken out after hydro-thermal, is rinsed well and dried up with deionized water.
Comparative sample 5
(1) pretreatment of matrix, it is identical with 1 step of embodiment (1).
(2) pretreated matrix in step (1) is carried out mixing molten iron heat, is prepared with deionized water and mix molten iron hot solution, Solution composition is 1mmol/L ferric trichlorides, 0.5mol/L ammonium fluorides, 0.2mol/L neopelexes, remaining for go from Sub- water, sample and prepared solution are added in hydrothermal reaction kettle, and hydrothermal reaction kettle volume is 25mL, add solution 10mL, Plot ratio 40%.
(3) by hydrothermal reaction kettle it is closed after be put into chamber type electric resistance furnace and heated, hydrothermal temperature is 120 DEG C, during hydro-thermal Between for 6 it is small when, sample is taken out after hydro-thermal, is rinsed well and dried up with deionized water, obtain Ni Ni-Fe LDH film layers.
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 films are obtained, microscopic appearance is to be laid on matrix (see Figure 12, Figure 13).
To Ni manufactured in the present embodiment3S2@Ni-Fe LDH analyse oxygen electro catalytic electrode and the surface topography of comparative sample 1 carries out table Sign, its SEM test result is as shown in Figure 1A, Figure 1B, and TEM test results are 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 basic unit, mutually flat OK, surface is smooth；Again by mixing molten iron heat treatment, 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 analyse oxygen electro catalytic electrode and the institutional framework of comparative sample 1 carries out table Sign, its 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 peaks do not occur in XRD.
To Ni manufactured in the present embodiment3S2@Ni-Fe LDH analyse oxygen electro catalytic electrode and the component of comparative sample 1 is 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, wherein Ni in the XPS tests of nanometer rods3S2Characteristic peak in the test chart of electrode intensity become Weak, the characteristic peak position of the Ni high 0.4eV after molten iron heat is mixed, illustrates that the average valence of Ni is hankered raising mixing molten iron.From Fig. 4 B As can be seen that Ni3S2There is characteristic peak in 712.1eV and 725eV in@Ni-Fe LDH electrodes, this is Fe3+Characteristic peak, show Fe3+Enter in LDH films.
To Ni manufactured in the present embodiment3S2The component of@Ni-Fe LDH analysis oxygen electro catalytic electrodes is characterized, its Raman spectrum Test result is as shown in figure 5, as can be seen from the figure remove Ni3S2Characteristic peak outside, in 495cm‐1And 575cm‐1Occur two Characteristic peak, is Fe respectively3+/Ni2+‐O‐Ni2+And Fe3+‐O‐Fe3+Characteristic peak, indicate the presence of Ni-Fe LDH.
Fig. 6 is Ni manufactured in the present embodiment3S2@Ni-Fe LDH analyse oxygen electro catalytic electrode and comparative sample 1, IrO2/ C electrodes 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 electrodes, Ni3S2Nanometer rods, Ni3S2@Ni-Fe LDH analysis oxygen electro-catalysis electricity Extremely show the catalytic performance of higher, but Ni3S2The catalytic performance of@Ni-Fe LDH analysis oxygen electro catalytic electrodes is substantially better than other Sample, analysis oxygen take-off potential is 1.42V vs RHE, and the analysis oxygen current density under 300mV overpotentials is 90mA/cm2, reach 10mA/cm2Overpotential needed for current density is 245mV.
Fig. 7 A are Ni manufactured in the present embodiment3S2@Ni-Fe LDH analyse oxygen electro catalytic electrode and IrO2/ C electrodes are 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‐ FeLDH analysis oxygen electro catalytic electrode overpotential for oxygen evolution in initial 2.5h is greatly lowered, this is Ni based compounds in constant current bar The process activated under part, after activation by 40 it is small when constant current reaction oxygen evolution potential only rise 5mV, IrO2/ C electrodes did not activate Journey, oxygen evolution potential rises 30mV after the constant current reaction of 10h.
Fig. 7 B prepare Ni for the present embodiment3S2@Ni-Fe LDH analyse 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, increase to 50mA/ cm25mA/cm is reduced per single order afterwards2, and 3min is kept, it is eventually returned to 5mA/cm2.It can be seen from the figure that per single order timing electricity The OER current potentials in position section are all sufficiently stable, and during current density rise and reduction, it is several with oxygen evolution potential during current density It is identical.It these results suggest that Ni3S2@Ni-Fe LDH analysis oxygen electro catalytic electrodes have good mass transfer ability, and electronics turns Move rapidly, gas diffusion effusion speed is fast.
Fig. 8 is Ni manufactured in the present embodiment3S2@Ni-Fe LDH analysis oxygen electro catalytic electrode, comparative sample 1 and IrO2/ C electrodes Tafel slope figures.It can be seen from the figure that Ni3S2The Tafel slopes of@Ni-Fe LDH analysis oxygen electro catalytic electrodes are significantly less than Ni3S2Nanometer rods and IrO2/ C electrodes, show Ni3S2The analysis oxygen current density of@Ni-Fe LDH analysis oxygen electro catalytic electrodes is with excessively electric Position rises and rises faster.
Fig. 9 is the SEM figures of comparative sample 2, it can be seen from the figure that the sample after anodic oxidation, in vulcanization water-heat process In, when hydrothermal solution does not add ethanol, the film of a layer plane structure is covered in nanometer rods, this coating is unfavorable for increase electricity Solve the contact area of liquid and nanorod structure.
Figure 10 is the SEM figures 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 vulcanizes, and adds nickel ion in the solution, can obtain the film layer of nano whiskers structure, but nanoneedle and basic unit's out of plumb, phase Mutually staggeredly, and there are ribbon, this pattern is unfavorable for the effusion of the gas produced in electrolysis water reaction.
Figure 12 is the SEM figures 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 in addition to the characteristic peak of matrix Ni, is occurred in three angles The characteristic peak of Ni-Fe LDH, shows that the molten iron of mixing in the present embodiment hankers that Ni-Fe LDH can be formed.
Figure 14 A, Figure 14 B represent comparative sample 1 and comparative sample 4 in 10mA/cm respectively2Gas evolution situation under current density, It can be seen from the figure that nickel sheet through anodic oxidation, vulcanizes the Ni of hydro-thermal process3S2Nano bar-shape film layer is in electrolysis elutriation oxygen catalysis The bubble separated out in reaction is smaller, and the nickel sheet film layer that sulphurous water is thermally treated resulting in additional nickel source solution is in electrolysis elutriation oxygen It is larger to go out in reaction the bubble separated out.This shows Ni of the nickel sheet through anodic oxidation, vulcanization hydro-thermal process3S2Nano bar-shape film layer exists The effusion of gas is more advantageous in electrolysis elutriation oxygen catalytic reaction, so as to promote continuing for reaction.
Embodiment 2
(1) pretreatment of matrix, it is identical with 1 step of embodiment (1).
(2) anodic oxidation of matrix, except bath composition is 2wt% ammonium fluorides, 85wt% phosphoric acid, remaining is deionization Outside water, other conditions are identical with 1 step of embodiment (2).
(3) sample is removed after the completion of anodic oxidation, it is clean using deionized water rinsing and dry up.
(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 fluorides, 5mol/L ethanol, remaining is deionized water, by sample and prepared solution Add in hydrothermal reaction kettle, hydrothermal reaction kettle volume is 25mL, adds solution 10mL, plot ratio 40%.
(5) by hydrothermal reaction kettle it is closed after be put into chamber type electric resistance furnace in heated, hydrothermal temperature be 140 DEG C, hydro-thermal When time is 6 small, sample is taken out after hydro-thermal, is rinsed well and dried up with deionized water, obtain nano bar-shape Ni3S2Film layer.
(6) the nano bar-shape Ni prepared to step (5)3S2Film layer carries out mixing molten iron heat, is prepared with deionized water and mixes molten iron heat Solution, solution composition are 2mmol/L ferric trichlorides, and 1mol/L ammonium fluorides, 0.5mol/L neopelexes, remaining is to go Ionized water.Sample and prepared solution are added in hydrothermal reaction kettle, hydrothermal reaction kettle volume is 25mL, adds solution 10mL, plot ratio 40%.
(7) by hydrothermal reaction kettle it is closed after be put into chamber type electric resistance furnace in heated, hydrothermal temperature be 110 DEG C, hydro-thermal When time is 8 small, sample is taken out after hydro-thermal, is rinsed well and dried up with deionized water, obtain Ni3S2@Ni-Fe LDH analyse 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-films are grown on Ni3S2On nanometer rods.It is 1.422V to analyse oxygen take-off potential Vs RHE, the analysis oxygen current density under 300mV overpotentials are 87mA/cm2, reach 10mA/cm2It is excessively electric needed for current density Position is 247mV, in 10mA/cm2Under current density through 40 it is small when constant current oxygen evolution reaction oxygen evolution potential only rise 5.6mV.
Embodiment 3
(1) pretreatment of matrix, it is identical with 1 step of embodiment (1).
(2) anodic oxidation of matrix：Anodic oxidation electrolyte is prepared by solvent of deionized water, bath composition is 0.5wt% ammonium fluorides, 75wt% phosphoric acid, remaining is deionized water.By the actual use part of step (1) pretreated matrix Immerse in electrolyte, retained part is connected with anode electrode.Anodic oxidation device is SP-150 electrochemical workstations, using three electricity Polar body system, matrix are used as to electrode as working electrode, platinum electrode, and saturated calomel electrode is as reference electrode.With 10mV/s's Speed boosts to 5V by open circuit potential, keeps constant pressure 5 minutes in 5V, 25 DEG C of electrolyte temperature.
(3) sample is removed after the completion of anodic oxidation, it is clean using deionized water rinsing and dry up.
(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 fluorides, the ethanol of 12mol/L, remaining is deionized water；By sample with preparing Vulcanization hydrothermal solution add hydrothermal reaction kettle in, hydrothermal reaction kettle volume be 25mL, addition solution 10mL, plot ratio 40%.
(5) by hydrothermal reaction kettle it is closed after be put into chamber type electric resistance furnace and heated, hydrothermal temperature is 100 DEG C, during hydro-thermal Between for 9 it is small when, reaction kettle is taken out from resistance furnace after hydro-thermal and is air-cooled to room temperature, opened reaction kettle taking-up sample, use deionization Water is rinsed well and dried up, and obtains nano bar-shape Ni3S2Film layer.
(6) the nano bar-shape Ni prepared to step (5)3S2Film layer carries out mixing molten iron heat, is prepared with deionized water and mixes molten iron heat Solution, solution composition are 0.5mmol/L ferric trichlorides, 0.1mol/L ammonium fluorides, 0.1mol/L neopelexes, remaining For deionized water.Sample and prepared solution are added in hydrothermal reaction kettle, hydrothermal reaction kettle volume is 25mL, adds solution 10mL, plot ratio 40%.
(7) by hydrothermal reaction kettle it is closed after be put into chamber type electric resistance furnace and heated, hydrothermal temperature is 130 DEG C, during hydro-thermal Between for 3 it is small when, reaction kettle is taken out from resistance furnace after hydro-thermal and is air-cooled to room temperature, opened reaction kettle taking-up sample, use deionization Water is rinsed well and dried up, and obtains Ni3S2@Ni-Fe LDH analyse 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-films are grown on Ni3S2On nanometer rods.It is 1.422V to analyse oxygen take-off potential Vs RHE, the analysis oxygen current density under 300mV overpotentials are 85mA/cm2, reach 10mA/cm2It is excessively electric needed for current density Position is 249mV, in 10mA/cm2Under current density through 40 it is small when constant current oxygen evolution reaction oxygen evolution potential only rise 6.1mV.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not limited to the embodiment Concrete mode, other any Spirit Essences without departing from the present invention with made under principle change, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (10)

  1. A kind of 1. Ni3S2@Ni-Fe LDH analyse the preparation method of oxygen electro catalytic electrode, it is characterised in that comprise the following steps：
    （1）Ni substrate is immersed in electrolyte, constant pressure anodized is carried out using three electrodes；
    （2）By step（1）Gained sample adds in hydrothermal reaction kettle with vulcanization hydrothermal solution and carries out vulcanization hydro-thermal process after processing, Rinsed well after processing with water, dry up, obtain nano bar-shape Ni3S2Film layer；
    （3）By step（2）Gained nano bar-shape Ni3S2Film layer carries out mixing molten iron with mixing in molten iron hot solution addition hydrothermal reaction kettle Heat treatment, is rinsed well after processing with water, is dried up, is obtained Ni3S2@Ni-Fe LDH analyse oxygen electro catalytic electrode.
  2. 2. preparation method according to claim 1, it is characterised in that step（1）Used in the anodized Electrolyte contains the ammonium fluoride of 0.5 ~ 2wt% and the phosphoric acid of 75 ~ 85wt%.
  3. 3. preparation method according to claim 1, it is characterised in that step（1）The anodized uses platinum electricity Pole is used as to electrode, and saturated calomel electrode is as reference electrode.
  4. 4. preparation method according to claim 1, it is characterised in that step（1）The constant pressure electricity of the 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.
  5. 5. preparation method according to claim 1, it is characterised in that step（2）The filling rate of the hydrothermal reaction kettle is 40%~50%；The temperature of the vulcanization hydro-thermal is 100 DEG C ~ 140 DEG C, when the time is 6 ~ 12 small.
  6. 6. preparation method according to claim 1, it is characterised in that step（2）Contain in the vulcanization hydrothermal solution The vulcanized sodium of 0.02 ~ 0.05mol/L, the ammonium fluoride of 0.1 ~ 0.2mol/L and the ethanol of 5 ~ 12mol/L.
  7. 7. preparation method according to claim 1, it is characterised in that step（3）The filling rate of the hydrothermal reaction kettle is 40%~50%；The temperature for mixing molten iron heat is 110 DEG C ~ 130 DEG C, when the time is 3 ~ 8 small.
  8. 8. preparation method according to claim 1, it is characterised in that step（3）Described mix in molten iron hot solution contains 0.5 The ferric trichloride of ~ 2mmol/L, the ammonium fluoride of 0.1 ~ 1mol/L and the neopelex of 0.1mol/L ~ 0.5mol/L.
  9. A kind of 9. Ni being prepared by claim 1 ~ 8 any one of them preparation method3S2@Ni-Fe LDH analysis oxygen electricity is urged Polarizing electrode.
  10. A kind of 10. Ni described in claim 93S2@Ni-Fe LDH analyse oxygen electro catalytic electrode as anode of electrolytic water oxygen evolution reaction Catalysis electrode application.
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