CN113089018A - Preparation method and new application of molybdenum disulfide-cobalt sulfide @ passivation layer - Google Patents

Preparation method and new application of molybdenum disulfide-cobalt sulfide @ passivation layer Download PDF

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CN113089018A
CN113089018A CN202110314965.8A CN202110314965A CN113089018A CN 113089018 A CN113089018 A CN 113089018A CN 202110314965 A CN202110314965 A CN 202110314965A CN 113089018 A CN113089018 A CN 113089018A
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molybdenum disulfide
cobalt sulfide
passivation layer
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nickel
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黄妞
刘朋
李佳乐
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China Three Gorges University CTGU
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • 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
    • 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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    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Abstract

The invention provides a preparation method of a molybdenum disulfide-cobalt sulfide @ passivation layer and application of the molybdenum disulfide-cobalt sulfide @ passivation layer in electrocatalytic oxygen evolution. Firstly, preparing a compound bottom layer containing molybdenum disulfide and cobalt sulfide by a solution method; and then a passivation layer for resisting alkalinity is loaded on the molybdenum disulfide-cobalt sulfide. The cobalt sulfide has good electrocatalytic oxygen evolution performance, and the composition of the molybdenum disulfide and the cobalt sulfide promotes the cracking of water on one hand and promotes the stability of the cobalt sulfide on the other hand; the stability can be further improved by further applying a passivation layer against alkali corrosion. The prepared molybdenum disulfide-cobalt sulfide @ passivation layer electrode has excellent electrocatalytic Oxygen Evolution Reaction (OER) activity.

Description

Preparation method and new application of molybdenum disulfide-cobalt sulfide @ passivation layer
Technical Field
The invention relates to an in-situ composite electrode and a preparation method thereof, belonging to the field of energy storage and conversion materials and devices.
Background
With the gradual depletion of conventional fossil fuels, the problems of energy shortage and global environmental pollution become increasingly severe. To alleviate such problems, the technology of preparing, converting and storing renewable green energy sources is very important. The hydrogen energy is considered to be a novel energy carrier with high efficiency due to the advantages of high energy conversion efficiency, cleanness, renewability, zero carbon emission and the like, wherein the electrocatalytic decomposition of water under alkaline conditions is considered to be one of the most potential ways for industrial application. The electrocatalysis for water decomposition needs high-efficiency electrocatalysts as anode and cathode materials respectively to catalyze Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER) to rapidly proceed at lower voltage difference. Among them, since OER is a four-electron process, the required overpotential is large, and the energy for electrocatalytic decomposition of water is mainly lost. In addition, the anode OER reaction is at a higher potential, and the catalyst is more prone to corrosion such as oxygen oxidation and oxygen substitution in an alkaline reaction, so that the stability requirement of the OER catalyst is higher. Currently, ruthenium oxide and iridium oxide with high performance and stability are ideal catalysts for OER, but the expensive price and rare reserves of ruthenium and iridium severely limit the large-scale commercial application of ruthenium and iridium. Therefore, the search and preparation of non-noble metal-based materials which are free of pollution, low in price and efficient and stable become an important research direction in the field of electrocatalytic water decomposition.
The cobalt sulfide is reported to have good OER performance, the molybdenum disulfide has good acid and alkali stability, and the composition of the molybdenum disulfide and the cobalt sulfide can improve the OER stability of the cobalt sulfide. In addition, degree functional theory calculation and related reports indicate that molybdenum disulfide with strong adsorption property to hydrogen protons or hydrogen atoms in water molecules and cobalt sulfide with strong adsorption property to hydroxyl groups or oxygen atoms in water molecules form a heterojunction, and the heterojunction interface synergistically improves the OER catalytic performance of the cobalt sulfide-based composite material. However, there is a problem that the sulfide is gradually converted into oxide/hydroxide/super hydroxide with exfoliation when it is operated in an alkaline high potential environment for a long time.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a core-shell in-situ composite material using molybdenum disulfide-cobalt sulfide as a core layer and a porous passivation layer as a shell layer. The core-shell structure has the advantages of low cost of raw materials, low equipment requirement, easy control of reaction conditions, simple production process, good consistency of formed products, small environmental pollution and the like, and the prepared electrode is an in-situ electrode, does not need subsequent slurry preparation coating and other processes, and has great significance for batch production of high-activity and high-stability OER catalysts. The preparation method comprises the following steps:
firstly, growing a molybdenum disulfide-cobalt sulfide compound bottom layer on the surface of a substrate. For example: dissolving molybdenum chloride, cobalt chloride and thiourea in a mixed solution of dimethylformamide and triton Tx100, wherein the concentration of cobalt ions is 300-900 mM, and the concentration ratio of the cobalt ions to the molybdenum ions to the thiourea is 1: 0.3-0.5: 1-3, wherein the volume ratio of Tx-100 to dimethylformamide is 0.1-0.5: 1, soaking a substrate such as foamed nickel or carbon paper or carbon cloth in the solution, taking out and drying the substrate, and annealing the substrate for 1 hour at 600 ℃ in a CVD furnace under a protective atmosphere.
And secondly, covering a porous passivation layer which is one of porous titanium dioxide, porous chromium oxide, nickel iron hydroxide and nickel iron phosphide on the bottom layer of the molybdenum disulfide-cobalt sulfide compound.
The porous titanium dioxide is obtained by corroding zinc oxide, namely zinc oxide in titanium dioxide. Dissolving zinc nitrate and tetrabutyl titanate in a mixed solution of ethanol, glacial acetic acid and water, stirring until the solution is clear, and then preserving heat for 3-4 h at 80-90 ℃ to obtain sol. The sol is coated on a molybdenum disulfide-cobalt sulfide base substrate and then dried in vacuum at 110 ℃ and 120 ℃. The sample coated with the zinc oxide-titanium oxide coating is put into 0.3-0.6M (preferably 0.5M) sulfuric acid and corroded for 20-24 h at room temperature to obtain the molybdenum disulfide-cobalt sulfide @ titanium oxide. Wherein the concentration of the zinc nitrate is 30-100 g/L; the mass ratio of tetrabutyl titanate to zinc nitrate is 0.3-0.6: 1; the volume ratio of the ethanol to the glacial acetic acid to the water is 90-95: 2-4: 1; and (4) vacuum drying for 8-12 h.
The porous chromium oxide is obtained by corroding zinc oxide-zinc oxide in chromium oxide. Dissolving zinc nitrate and chromium acetate in a mixed solution of ethanol, glacial acetic acid and water, stirring until the mixed solution is clear, and then preserving heat for 3-4 h at the temperature of 80-90 ℃ to obtain sol. The sol is coated on a molybdenum disulfide-cobalt sulfide base substrate and then dried in vacuum at 110 ℃ and 120 ℃. The sample coated with the zinc oxide-chromium oxide coating is put into 0.3-0.6M (preferably 0.5M) sulfuric acid and corroded for 20-24 h at room temperature to obtain the product with the growth of molybdenum disulfide-cobalt sulfide @ chromium oxide. Wherein the concentration of the zinc nitrate is 30-100 g/L; the mass ratio of the chromium acetate to the zinc nitrate is 0.3-0.6: 1; the volume ratio of the ethanol to the glacial acetic acid to the water is 90-95: 2-4: 1; and (4) vacuum drying for 8-12 h.
The preparation method of the nickel hydroxide iron comprises the following steps of preparing an aqueous solution of nickel nitrate and ferric nitrate, wherein the total concentration of metal ions is 5-15 mM, and the concentration ratio of nickel ions to iron ions is as follows: 2-3: 1. and electrodepositing for 15-60 min at-1V by using the aqueous solution as an electrolyte solution, a conductive substrate on which molybdenum disulfide-cobalt sulfide grows as a working electrode and Ag/AgCl as a reference electrode. The prepared nickel iron hydroxide is characterized in that the nickel iron hydroxide is a nickel iron hydroxide nanosheet array which grows nearly vertical to the bottom layer of the molybdenum disulfide-cobalt sulfide, and the molybdenum disulfide-cobalt sulfide can be contacted with electrolyte of electrolytic water through gaps left by the nanosheets.
The specific preparation method of the nickel-iron phosphide comprises the following steps of preparing the nickel-iron hydroxide by the method and then adding 0.03-0.1M NaH2PO2Heating the solution in water bath at 85-98 ℃ for 2-8 h.
Drawings
FIG. 1 is a graph showing the OER linear voltammetry scan (LSV) measured on the sample prepared in example 1.
FIG. 2 is a graph showing the OER linear voltammetry scan (LSV) measured for the sample prepared in example 2.
FIG. 3 is a plot of the OER linear voltammetry scans (LSV) measured on the samples prepared in example 3.
FIG. 4 is a plot of the OER linear voltammetry scans (LSV) measured on the samples prepared in example 4.
FIG. 5 is a plot of the OER linear voltammetry scans (LSV) measured on the samples prepared in example 5.
FIG. 6 is a plot of the OER linear voltammetry scans (LSV) measured on the samples prepared in example 6.
FIG. 7 is a plot of the OER linear voltammetry scans (LSV) measured on the samples prepared in example 7.
FIG. 8 is a plot of the OER linear voltammetry scans (LSV) measured on the samples prepared in example 8.
FIG. 9 is an SEM photograph of a sample prepared in example 1, wherein A is an SEM photograph magnified by 1 ten thousand magnification and B is an SEM photograph magnified by 5 ten thousand magnification.
Fig. 10 is an SEM image a at 1 ten thousand magnification and an SEM image B at 5 ten thousand magnification of the sample prepared in example 6.
FIG. 11 is an SEM photograph of a sample prepared in example 7, wherein A is an SEM photograph magnified by 1 ten thousand magnification and B is an SEM photograph magnified by 5 ten thousand magnification.
Fig. 12 is an SEM image a at 1 ten thousand magnification and an SEM image B at 5 ten thousand magnification of the sample prepared in example 8.
Fig. 13 is an XRD pattern of example 6, example 7, and example 8.
Fig. 14 is a linear voltammogram (LSV) of the Hydrogen Evolution Reaction (HER) measured for the sample obtained in example 6.
Characterizing conditions
The OER test method in the embodiment of the invention comprises the following steps: the method is characterized in that a molybdenum disulfide-cobalt sulfide @ passivation layer in-situ electrode is taken as a working electrode, a carbon rod is taken as a counter electrode, a saturated Hg/HgO electrode is taken as a reference electrode, and the used electrolytes are as follows: 1M aqueous KOH solution, scanning speed 5 mV/s. In the OER test, oxygen was bubbled in so that the oxygen was naturally saturated in 1M aqueous KOH and was accompanied by stirring at 200 rpm during the test. The saturated Hg/HgO electrode was corrected with a reversible hydrogen electrode, and the potentials described hereinafter are all relative to the reversible hydrogen electrode. The electric potential is automatically carried out by using the Shanghai Chen chemical workstation in the LSV testIR) And (6) compensation. An X-ray diffraction (SEM) pattern of the sample was obtained using a SMART LAB-9 type X-ray diffractometer. Scanning electron microscope (XRD) images were acquired using an aspect F50 scanning electron microscope (FEI America).
Detailed Description
Example 1:
0.0819 g of MoCl were weighed5，0.2141 g CoCl2∙6H2Dissolving O, 0.2284 g thiourea in 2 mL N-N dimethylformamide, finally adding 1 mL Tx-100 to obtain a precursor solution, immersing a hydrophilic Dongli carbon paper (CFP) substrate in the precursor solution for 30 min, taking out the substrate, drying the substrate at 80 ℃ for 30 min, carrying out CVD annealing, and carrying out N-Dimethylformamide (DMF) annealing2And (3) obtaining Dongli CFP/molybdenum disulfide-cobalt sulfide at 600 ℃ for 1 h.
FIG. 1 is an OER linear voltammetric sweep (LSV) measured on the sample prepared in example 1. The current density when the electrode passes through is 100 mA/cm2When the oxygen is generated by OER in the alkaline aqueous solution, the corresponding overpotential is 318 mV.
Fig. 9 is an SEM image of the sample prepared in example 1. It can be seen that the composite particles formed by molybdenum disulfide and cobalt sulfide are densely coated on the surface of the carbon fiber substrate. The flaky molybdenum disulfide and cobalt sulfide compound with low adhesion on the surface falls off in the subsequent corrosion or electrodeposition process, and only the bottom layer tightly covered on the carbon fibers is reserved. This is reasonably evident from later analysis of the SEM and XRD results.
Example 2:
0.0819 g of MoCl were weighed5，0.2141 g CoCl2∙6H2Dissolving O, 0.2284 g thiourea in 2 mL N-N dimethylformamide, finally adding 1 mL Tx-100 to obtain a precursor solution, immersing the hydrophilic Dongli carbon paper CFP substrate in the precursor solution for 30 min, then taking out the substrate, drying the substrate at 80 ℃ for 30 min, carrying out CVD annealing, and carrying out N-Dimethylformamide (DMF)2And (3) obtaining Dongli CFP/molybdenum disulfide-cobalt sulfide at 600 ℃ for 1 h.
Preparing solution A: a graduated cylinder measures 73.3 mL of ethanol and 2.4 mL of glacial acetic acid, and places them in a beaker and mixes well, stirring solution A while adding 7.08 g of zinc nitrate, 3.3 mL of tetrabutyl titanate. Preparing a solution B: 20 mL ethanol +1 mL water. And slowly dripping the solution B into the solution A while stirring, then putting the solution into a hydrothermal box, keeping the temperature for 4 hours at 80 ℃, lifting the Dongli CFP/molybdenum disulfide-cobalt sulfide in the kept mixed solution for five times, and keeping the solution at the temperature of 120 ℃ for 12 hours after the solution is completely dried. And putting the sample into 0.5M sulfuric acid, corroding for 24 hours at room temperature, washing the sulfuric acid on the surface by deionized water, and drying to obtain Dongli CFP/molybdenum disulfide-cobalt sulfide @ porous titanium oxide.
FIG. 2 is an OER linear voltammetric sweep (LSV) measured on the sample prepared in example 2. The current density when the electrode passes through is 100 mA/cm2When the reaction is carried out, the overpotential corresponding to the oxygen generated by OER in the alkaline aqueous solution is 381 mV; when the electrode passes through the current density of 400 mA/cm2When the oxygen is generated by OER in the alkaline aqueous solution, the corresponding overpotential is 467 mV. Compared with Dongli CFP/molybdenum disulfide-cobalt sulfide without a passivation layer, the OER activity of the composite is reduced, but the stability of the composite is improved due to the introduction of titanium oxide.
Example 3:
0.0819 g of MoCl were weighed5，0.2141 g CoCl2∙6H2O, 0.2284 g of thiourea was dissolved in 2 mL of N-Finally adding 1 mL of Tx-100 into N-dimethylformamide to obtain a precursor solution, immersing the hydrophilic Dongli carbon paper CFP substrate into the precursor solution for 30 min, taking out the substrate, drying the substrate at 80 ℃ for 30 min, and carrying out CVD annealing, wherein N is2And (3) obtaining Dongli CFP/molybdenum disulfide-cobalt sulfide at 600 ℃ for 1 h.
Solution A was prepared by measuring 73.3 mL of ethanol and 2.4 mL of glacial acetic acid in a graduated cylinder, mixing them well in a beaker, and stirring solution A while adding 7.08 g of zinc nitrate and 2.22 g of chromium acetate. Preparing a solution B: 20 mL ethanol +1 mL water. And slowly dripping the solution B into the solution A while stirring. And (3) lifting the Dongli CFP/molybdenum disulfide-cobalt sulfide in the heat-preserved mixed solution for five times, and after the Togli CFP/molybdenum disulfide-cobalt sulfide is completely dried, putting the Togli CFP/molybdenum disulfide-cobalt sulfide in a vacuum drying oven at the temperature of 120 ℃ and preserving the heat for 12 hours. And putting the sample into 0.5M sulfuric acid, corroding for 24 hours at room temperature, washing the sulfuric acid on the surface by deionized water, and drying to obtain Dongli CFP/molybdenum disulfide-cobalt sulfide @ chromium oxide.
FIG. 3 is an OER linear voltammetric sweep (LSV) measured for the sample prepared in example 3. The current density when the electrode passes through is 100 mA/cm2When the reaction is carried out, the overpotential corresponding to the oxygen generation of OER in the alkaline aqueous solution is 363 mV. Compared with Dongli CFP/molybdenum disulfide-cobalt sulfide without a passivation layer, the OER activity of the material is reduced, but the stability of the material is improved due to the introduction of chromium oxide.
Example 4:
0.0819 g of MoCl were weighed5，0.2141 g CoCl2∙6H2Dissolving O, 0.2284 g thiourea in 2 mL N-N dimethylformamide, finally adding 1 mL Tx-100 to obtain a precursor solution, immersing the hydrophilic Dongli carbon paper CFP substrate in the precursor solution for 30 min, then taking out the substrate, drying the substrate at 80 ℃ for 30 min, carrying out CVD annealing, and carrying out N-Dimethylformamide (DMF)2And (3) obtaining Dongli CFP/molybdenum disulfide-cobalt sulfide at 600 ℃ for 1 h.
Configuration of 6 mM Ni (NO)3)2And 2 mM Fe (NO)3)3And performing electrodeposition on the treated Dongli CFP/molybdenum disulfide-cobalt sulfide for 45 min under the condition that the working voltage is-1V by utilizing an electrochemical workstation and an Ag/AgCl electrode as a reference electrode. Washed by deionized water and dried to obtain Dongli CFP/molybdenum disulfide-cobalt sulphide @ nickel iron hydroxide.
FIG. 4 is an OER linear voltammetric sweep (LSV) measured for the sample prepared in example 4. The current density when the electrode passes through is 100 mA/cm2When the oxygen is generated by OER in the alkaline aqueous solution, the corresponding overpotential is 280 mV. Compared with Dongli CFP/molybdenum disulfide-cobalt sulfide without a passivation layer, the OER activity and stability of the material are improved.
Example 5:
0.0819 g of MoCl were weighed5，0.2141 g CoCl2∙6H2Dissolving O, 0.2284 g thiourea in 2 mL N-N dimethylformamide, finally adding 1 mL Tx-100 to obtain a precursor solution, immersing the hydrophilic Dongli carbon paper CFP substrate in the precursor solution for 30 min, then taking out the substrate, drying the substrate at 80 ℃ for 30 min, carrying out CVD annealing, and carrying out N-Dimethylformamide (DMF)2And (3) obtaining Dongli CFP/molybdenum disulfide-cobalt sulfide at 600 ℃ for 1 h.
Configuration of 6 mM Ni (NO)3)2And 2 mM Fe (NO)3)3And performing electrodeposition on the treated Dongli CFP/molybdenum disulfide-cobalt sulfide for 45 min under the condition that the working voltage is-1V by utilizing an electrochemical workstation and an Ag/AgCl electrode as a reference electrode. Washed with deionized water, dried, and washed with 0.05M NaH2PO2Heating the solution in a water bath at 90 ℃ for 4 h, washing with deionized water, and drying to obtain Dongli CFP/molybdenum disulfide-cobalt sulfide @ nickel iron phosphide.
FIG. 5 is an OER linear voltammetric sweep (LSV) measured for the sample prepared in example 5. The current density when the electrode passes through is 100 mA/cm2When the oxygen is generated by OER in the alkaline aqueous solution, the corresponding overpotential is 294 mV.
Example 6:
0.0819 g of MoCl were weighed5，0.2141 g CoCl2∙6H2Dissolving O, 0.2284 g thiourea in 2 mL N-N dimethylformamide, finally adding 1 mL Tx-100 to obtain a precursor solution, immersing the hydrophilic Hesen carbon paper CFP substrate in the precursor solution for 30 min, then taking out the precursor solution, drying the precursor solution for 30 min at 80 ℃, performing CVD annealing, and performing N-dimethylformamide (N-dimethylformamide)2And (4) obtaining Heson CFP/molybdenum disulfide-cobalt sulfide at the atmosphere of 600 ℃ for 1 h.
Solution A was prepared by measuring 73.3 mL of ethanol and 2.4 mL of glacial acetic acid in a graduated cylinder, mixing them well in a beaker, and stirring solution A while adding 7.08 g of zinc nitrate and 2.22 g of chromium acetate. Preparing a solution B: 20 mL ethanol +1 mL water. And slowly dripping the solution B into the solution A while stirring. And lifting the Hesen CFP/molybdenum disulfide-cobalt sulfide in the heat-preserved mixed solution for five times, and after the mixture is completely dried, putting the mixture into a vacuum drying oven for heat preservation at the temperature of 120 ℃ for 12 hours. And putting the sample into 0.5M sulfuric acid, corroding for 24 hours at room temperature, washing the sulfuric acid on the surface by using deionized water, and drying to obtain Hesen CFP/molybdenum disulfide-cobalt sulfide @ chromium oxide.
FIG. 6 is an OER linear voltammetric sweep (LSV) measured for the sample prepared in example 6. The current density when the electrode passes through is 100 mA/cm2When the oxygen is generated by the OER in the alkaline aqueous solution, the corresponding overpotential is 312 mV.
In addition, the hydrogen evolution performance (HER) linear voltammetric scan (LSV) of the sample prepared in example 6 was also tested, as shown in fig. 14. The current density when the electrode passes through is 100 mA/cm2In alkaline aqueous solution, the overpotential corresponding to the production of hydrogen by HER is 216 mV. Since HER is a 2 electron process more complex than the OER four electron process, the overpotential required for HER reactions is typically much smaller. The OER performance (minus 300 mV) of the sample prepared by the embodiment is comparable with that of ruthenium oxide, iridium oxide and nickel-iron hydroxide; and the HER (over potential is more than 200 mV) has a larger difference with high-performance HER catalysts such as platinum and the like, so the sample is mainly used for catalyzing OER.
Fig. 10 is an SEM image of the sample prepared in example 6. It can be seen that the granular chromium oxide completely covered the underlying molybdenum disulfide-cobalt sulfide layer. Since there is no protrusion, it is presumed that the original flaky molybdenum disulfide and cobalt sulfide composite with low adhesion falls off in the subsequent corrosion.
Figure 13 illustrates the XRD pattern of the sample prepared in example 6. As can be seen from the figure, the main component of the composite electrode was Co9S8(PDF # 02-1459), and no significant XRD peaks were observed due to the low molybdenum disulfide and chromium oxide content and low crystallinity. XRD result analysis shows that molybdenum disulfide-cobalt sulfide bottom is generated in the corrosion processThe layer remains and the surface layer remains a chromium oxide layer after corrosion by zinc oxide.
Example 7:
0.0819 g of MoCl were weighed5，0.2141 g CoCl2∙6H2Dissolving O, 0.2284 g thiourea in 2 mL N-N dimethylformamide, finally adding 1 mL Tx-100 to obtain a precursor solution, immersing the hydrophilic Hesen carbon paper CFP substrate in the precursor solution for 30 min, then taking out the precursor solution, drying the precursor solution for 30 min at 80 ℃, performing CVD annealing, and performing N-dimethylformamide (N-dimethylformamide)2And (4) obtaining Heson CFP/molybdenum disulfide-cobalt sulfide at the atmosphere of 600 ℃ for 1 h.
Configuration of 6 mM Ni (NO)3)2And 2 mM Fe (NO)3)3And (3) carrying out electrodeposition on the treated Heson CFP/molybdenum disulfide-cobalt sulfide for 45 min by utilizing an electrochemical workstation and using an Ag/AgCl electrode as a reference electrode under the condition that the working voltage is-1V. And washing with deionized water and drying to obtain Hesen CFP/molybdenum disulfide-cobalt sulfide @ nickel iron hydroxide.
FIG. 7 is an OER linear voltammetric sweep (LSV) measured for the sample prepared in example 7. The current density when the electrode passes through is 100 mA/cm2When the reaction is carried out, the overpotential corresponding to the oxygen generated by OER in the alkaline aqueous solution is 270 mV; when the electrode passes through the current density of 400 mA/cm2In this case, the overpotential required for the OER to produce oxygen in the aqueous alkaline solution was also small, 317 mV.
FIG. 11 is an SEM photograph of a sample prepared in example 7. It can be seen that the sheet nickel iron hydroxide forms a network array which grows almost vertically on and covers the bottom layer of molybdenum disulfide-cobalt sulfide.
Figure 13 illustrates the XRD pattern of the sample prepared in example 7. As can be seen from the figure, the main component of the composite electrode was Co9S8(PDF # 02-1459), and no significant XRD peaks were observed due to the low molybdenum disulfide content and low hydroxide crystallinity. XRD result analysis shows that the bottom layer of molybdenum disulfide-cobalt sulfide still remains and the surface layer is nickel iron hydroxide in the corrosion process. Because nitrate radicals are nitrite and hydroxyl in situ under negative potential, hydroxyl reacts with ferronickel ions to generate layered (often sheet-shaped) ferronickel hydroxide.
Example 8:
0.0819 g of MoCl were weighed5，0.2141 g CoCl2∙6H2Dissolving O, 0.2284 g thiourea in 2 mL N-N dimethylformamide, finally adding 1 mL Tx-100 to obtain a precursor solution, immersing the hydrophilic Hesen carbon paper CFP substrate in the precursor solution for 30 min, then taking out the precursor solution, drying the precursor solution for 30 min at 80 ℃, performing CVD annealing, and performing N-dimethylformamide (N-dimethylformamide)2And (4) obtaining Heson CFP/molybdenum disulfide-cobalt sulfide at the atmosphere of 600 ℃ for 1 h.
Configuration of 6 mM Ni (NO)3)2And 2 mM Fe (NO)3)3And (3) carrying out electrodeposition on the treated Heson CFP/molybdenum disulfide-cobalt sulfide for 45 min by utilizing an electrochemical workstation and using an Ag/AgCl electrode as a reference electrode under the condition that the working voltage is-1V. Washed with deionized water, dried, and washed with 0.05M NaH2PO2Heating the solution in a water bath at 90 ℃ for 4 h, washing with deionized water, and drying to obtain Hesen CFP/molybdenum disulfide-cobalt sulfide @ nickel iron phosphide.
FIG. 8 is an OER linear voltammetric sweep (LSV) measured for the sample prepared in example 8. The current density when the electrode passes through is 100 mA/cm2When the reaction is carried out, the overpotential corresponding to the oxygen generated by OER in the alkaline aqueous solution is 283 mV; when the electrode passes through the current density of 400 mA/cm2When the reaction is carried out, the overpotential corresponding to the oxygen generation of OER in the alkaline aqueous solution is 333 mV.
FIG. 12 is an SEM photograph of a sample prepared in example 8. The figure shows the flaky nickel iron phosphide (Ni)3Fe-P) forms a network array that grows almost vertically on and covers the bottom layer of molybdenum disulfide-cobalt sulfide.
Figure 13 illustrates the XRD pattern of the sample prepared in example 8. As can be seen from the figure, the main component of the composite electrode was Co9S8(PDF # 02-1459), and no significant XRD peaks were observed due to the low molybdenum disulfide content and the low nickel iron phosphide crystallinity. XRD result analysis shows that the bottom layer of molybdenum disulfide-cobalt sulfide is still remained and the surface layer is made of nickel phosphide.

Claims (10)

1. A preparation method of a molybdenum disulfide-cobalt sulfide @ passivation layer in-situ electrode is characterized in that the electrode is of a core-shell structure with the molybdenum disulfide-cobalt sulfide as a core layer and a porous passivation layer as a shell layer, and the specific preparation method comprises the following steps:
(1) growing a molybdenum disulfide-cobalt sulfide compound on the surface of the substrate;
(2) and covering a porous passivation layer on the bottom layer of the molybdenum disulfide-cobalt sulfide compound.
2. The method of claim 1 wherein said porous passivation layer comprises any one of porous titanium oxide, porous chromium oxide, nickel iron hydroxide, and nickel iron phosphide.
3. The preparation method of the molybdenum disulfide-cobalt sulfide @ passivation layer in-situ electrode as claimed in claim 2, wherein the zinc nitrate and tetrabutyl titanate are dissolved in a mixed solution of ethanol, glacial acetic acid and water, and the mixed solution is stirred until the mixed solution is clear and then is subjected to heat preservation at 80-90 ℃ for 3-4 h to obtain sol; coating the sol on a molybdenum disulfide-cobalt sulfide base, drying in vacuum, putting into a sulfuric acid solution, and corroding at room temperature to obtain the in-situ electrode on which the molybdenum disulfide-cobalt sulfide @ titanium oxide grows.
4. The preparation method of the molybdenum disulfide-cobalt sulfide @ passivation layer in-situ electrode according to claim 3, wherein the mass ratio of tetrabutyl titanate to zinc nitrate is 0.3-0.6: 1, simultaneously controlling the concentration of zinc nitrate to be 30-100 g/L; the volume ratio of the ethanol to the glacial acetic acid to the water is 90-95: 2-4: 1; the molar concentration of the sulfuric acid solution is 0.3-0.6M.
5. The method of claim 3 wherein said tetrabutyl titanate is replaced with chromium acetate to produce molybdenum disulfide-cobalt sulfide @ chromium oxide.
6. The method for preparing the molybdenum disulfide-cobalt sulfide @ passivation layer in-situ electrode according to claim 2, wherein the passivation layer is nickel iron hydroxide, and the molybdenum disulfide-cobalt sulfide @ nickel iron hydroxide is obtained by electrodeposition at-1 to-2V for 15 to 60 min by using a substrate with a molybdenum disulfide-cobalt sulfide composite growing on the surface as a working electrode, Ag/AgCl as a reference electrode and an aqueous solution of nickel nitrate and iron nitrate as an electrolyte.
7. The method for preparing the molybdenum disulfide-cobalt sulfide @ passivation layer in-situ electrode as claimed in claim 6, wherein the total concentration of metal ions in the aqueous solution of nickel nitrate and ferric nitrate is 5-15 mM, and the concentration ratio of nickel ions to iron ions is as follows: 2-3: 1.
8. the method of claim 7, wherein said passivation layer is nickel-iron phosphide, and said molybdenum disulfide-cobalt sulfide @ nickel-iron hydroxide is added in NaH2PO2Heating the solution in water bath at 85-98 ℃ for 2-8 h.
9. The method of claim 8, wherein the NaH is a component of the in situ electrode comprising the molybdenum disulfide, cobalt sulfide and passivation layer2PO2The concentration of the solution is 0.03-0.1M.
10. Use of a molybdenum disulphide-cobalt sulphide @ passivation layer in situ electrode prepared according to any one of claims 1 to 9 in an electrocatalytic oxygen evolution reaction.
CN202110314965.8A 2021-03-24 2021-03-24 Preparation method and new application of molybdenum disulfide-cobalt sulfide @ passivation layer Pending CN113089018A (en)

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