CN111889117B - Core-shell copper selenide @ nickel-iron hydrotalcite-like electrocatalyst, preparation method thereof and application of electrocatalyst in water electrolysis - Google Patents
Core-shell copper selenide @ nickel-iron hydrotalcite-like electrocatalyst, preparation method thereof and application of electrocatalyst in water electrolysis Download PDFInfo
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000011258 core-shell material Substances 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 22
- 238000005868 electrolysis reaction Methods 0.000 title claims description 5
- 239000010949 copper Substances 0.000 claims abstract description 148
- 239000011669 selenium Substances 0.000 claims abstract description 74
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 39
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 39
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000002070 nanowire Substances 0.000 claims abstract description 28
- 229910000863 Ferronickel Inorganic materials 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000004070 electrodeposition Methods 0.000 claims abstract description 13
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 6
- IRPLSAGFWHCJIQ-UHFFFAOYSA-N selanylidenecopper Chemical compound [Se]=[Cu] IRPLSAGFWHCJIQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 19
- 239000006260 foam Substances 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000002135 nanosheet Substances 0.000 abstract description 29
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 239000002131 composite material Substances 0.000 abstract description 6
- 239000008151 electrolyte solution Substances 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000007789 gas Substances 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 19
- 238000001075 voltammogram Methods 0.000 description 10
- 238000000151 deposition Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 238000011160 research Methods 0.000 description 5
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- 239000000463 material Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- -1 Transition metal selenides Chemical class 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 238000000975 co-precipitation Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012353 t test Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- B01J35/397—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- 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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a core-shell Cu2Se @ NiFe-LDH electrocatalyst, and a preparation method and application thereof. Firstly, using foamed copper as substrate, in the alkaline medium and adopting chemical oxidation method to make in-situ growth of Cu (OH) on its surface2Selenizing the nano-wire by selenium powder in a tube furnace to convert the nano-wire into copper selenide nano-wire, finally growing the nickel-iron hydrotalcite nano-sheet on the surface of the nano-wire by adopting an electrodeposition method, and preparing the core-shell copper selenide @ nickel-iron hydrotalcite nano-sheet electrocatalyst by adopting a two-step method of gas phase selenization and electrodeposition. The obtained core-shell copper selenide @ ferronickel hydrotalcite nanosheet catalyst is in a nanowire shape, and the diameter of the core-shell copper selenide @ ferronickel hydrotalcite nanosheet catalyst is 150-250 nm; with Cu2Se is taken as a core, NiFe-LDH sheets are taken as shells, and the thickness of the NiFe-LDH sheets is less than 10 nm; the catalytic activity of the nickel-iron hydrotalcite nanosheets and the composite materials thereof in the 1mol/L KOH electrolyte solution through oxygen evolution reaction, hydrogen evolution reaction and full hydrolysis is higher than that of the nickel-iron hydrotalcite nanosheets and the composite materials thereof prepared by other traditional methods.
Description
The technical field is as follows:
the invention relates to a core-shell copper selenide @ ferronickel hydrotalcite (Cu) for effectively improving the efficiency of water electrolysis 2Se @ NiFe-LDH) electricityThe invention relates to a catalyst and a preparation method thereof, and relates to a catalytic action of a core-shell copper selenide @ nickel iron hydrotalcite electrocatalyst prepared by the preparation method on an Oxygen Evolution Reaction (OER) and a Hydrogen Evolution Reaction (HER) under an alkaline condition, belonging to the field of electrocatalysis.
The background art comprises the following steps:
the electrolysis of water has great significance for reducing petrochemical energy requirements and protecting the environment. However, in acidic and alkaline electrolytes, the electrolyzed water needs to break the O-H bond and release electrons to form O ═ O double bonds, and the kinetic process is very slow, usually requiring a potential higher than 1.23V, i.e. a large overpotential. Therefore, it is desirable to use a high activity catalyst to reduce the overpotential to achieve efficient water splitting. Oxygen Evolution Reaction (OER) is the bottleneck for water decomposition, albeit with noble metal catalysts, such as RuO2And IrO2However, it is expensive, scarce, and requires a large overpotential to drive the OER. Therefore, the development of the efficient, abundant and cheap OER non-noble metal catalyst is one of the subjects of the current renewable energy research.
Transition double metal hydroxides (LDHs) have potential application values due to their compositional diversity and stability. Studies have shown that bimetallic NiFe-LDH has higher catalytic activity and lower overpotential than LDH containing only a single Ni or Fe component. However, the HER performance of NiFe-LDH is not satisfactory. Research shows that strong interaction between transition metal hydroxide and other metal compounds plays an important role in the structure and electrochemical properties of the constructed composite. Transition metal selenides are considered a promising class of support materials because they have unique electronic configurations and reasonably good catalytic activity, and can serve to modulate the OER and HER properties of LDHs. The specific surface area, the conductivity and the stability of the composite catalyst can be improved through reasonable structural design, and the electrocatalytic activity of the composite catalyst is further promoted.
In the invention, Cu2Se is used as a supporting carrier, and a core-shell Cu is prepared by an electrodeposition method2Se @ ferronickel hydrotalcite-like compound Cu2Se @ NiFe-LDH. The invention controls the deposition time, the concentration and the proportion of electrolyte metal ions to the deposition conditionsOptimizing, namely carrying out electrochemical performance test on CuSe @ NiFe-LDH with different deposition time, and comparatively analyzing the influence of the deposition time on the appearance and the catalytic performance of the catalyst; cu produced by different metal ion concentrations2Se @ NiFe-LDH performance test is carried out, and the influence of the metal ion concentration on the appearance and the catalytic performance of the catalyst is comparatively analyzed; cu produced by different metal ion ratios2Se @ NiFe-LDH performance test is carried out, the influence of the metal ion ratio on the morphology and the catalytic performance of the catalyst is contrastively analyzed, the optimal condition of electrodeposition is obtained, and the core-shell Cu is prepared2Se @ NiFe-LDH electrode material and system research on the electrolytic water property of the material, and research work related to the material is not reported.
The invention content is as follows:
aiming at the defects of the prior art and the requirements of research and application in the field, one of the purposes of the invention is to provide a core-shell copper selenide @ nickel iron hydrotalcite-like electrocatalyst which is characterized in that the catalyst takes foam copper as a substrate, and Cu (OH) is grown on the surface of the catalyst in situ by a chemical oxidation method in an alkaline medium 2Selenizing the nano-wire by selenium powder in a tube furnace to be converted into a copper selenide nano-wire, and finally growing the nickel-iron hydrotalcite on the surface of the nano-wire by an electrodeposition method; the copper foam is CF, the copper selenide is Cu2Se, nickel-iron hydrotalcite is recorded as NiFe-LDH, and copper selenide @ nickel-iron hydrotalcite is recorded as Cu2Se@NiFe-LDH；
The second purpose of the invention is to provide a preparation method of the core-shell copper selenide @ ferronickel hydrotalcite electrocatalyst, which comprises the following steps:
(1)Cu2preparation of Se/CF
Soaking commercial foam copper with the specification of 3cm multiplied by 4cm in a hydrochloric acid solution with the concentration of 37% for 10 minutes, and washing for a plurality of times by using deionized water and absolute ethyl alcohol; the cleaned foamy copper is put into 80mL NaOH and (NH)4)2S2O8The mixed solution is soaked for 20min, so that light blue Cu (OH) grows on the surface in situ2Nanowire, taking out Cu (OH) grown thereon2Washing the foam copper of the nanowire with deionized water, and drying in an oven at 60 ℃ for 6 h; will be provided withDried Cu (OH)2Placing the nanowire in a tube furnace, simultaneously placing 0.1g selenium powder at the front end of the tube furnace, heating to 400 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, keeping for 30min, taking out a sample after the tube furnace is naturally cooled, and washing with deionized water and ethanol for several times to obtain Cu 2Se/CF, drying for later use;
(2)Cu2preparation of Se @ NiFe-LDH/CF
With Cu2Se/CF as working electrode, Pt wire electrode as counter electrode, saturated calomel electrode as reference electrode, and Ni (NO) as electrolyte3)2And FeSO4Electrifying the mixed aqueous solution for 60-150 s under the condition that the potential is-1.0V to perform an electrodeposition reaction so as to grow NiFe-LDH on the surface of the mixed aqueous solution, and preparing the nuclear shell Cu2Se @ NiFe-LDH/CF catalyst;
wherein NaOH and (NH) in step (1)4)2S2O8NaOH and (NH)4)2S2O8The molar concentrations of the compounds are respectively 2.5 and 0.125 mol/L; ni (NO) in step (2)3)2And FeSO4The total concentration of metal ions in the mixed aqueous solution is 0.15-0.45 mol/L, Ni (NO)3)2And FeSO41-6: 2.
the electrocatalyst prepared by the preparation method is in a nanowire shape, and the diameter of the electrocatalyst is 150-250 nm; with Cu2Se is taken as a core, NiFe-LDH sheets are taken as shells, and the thickness of the NiFe-LDH sheets is less than 10 nm.
Core-shell Cu prepared by the above preparation method2Se @ NiFe-LDH electrocatalyst suitable for catalyzing oxygen evolution reaction and hydrogen evolution reaction in alkaline electrolyte, and the application is to use core-shell Cu2The Se @ NiFe-LDH electrocatalyst is added into a 1mol/L KOH solution to be used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, and the catalytic activity of oxygen evolution reaction and hydrogen evolution reaction of the Se @ NiFe-LDH electrocatalyst and the full water-splitting performance of the Se @ NiFe-LDH electrocatalyst when the Se @ NiFe-LDH electrocatalyst is used as a dual-function electrode are tested.
Compared with the prior art, the invention has the main beneficial effects and advantages that:
(1) core of the inventionShell shaped Cu2The preparation method of the Se @ NiFe-LDH electrocatalyst overcomes the defects of aggregation, large particle size, wide particle size distribution range, small specific surface area and the like existing in the preparation of the nickel-iron hydrotalcite by the traditional coprecipitation method, and has the characteristics of large specific surface area, uniform size, thin lamella, good mechanical stability and the like.
(2) The core-shell Cu2Se @ NiFe-LDH electrocatalyst, Se element changes the electronic structure of Cu, so that Cu2Se has good conductivity and catalytic activity, Cu2The Se support obviously improves the conductivity and the dispersibility of the NiFe-LDH material and improves the catalytic performance.
(3) The core-shell Cu2The preparation method of the Se @ NiFe-LDH electrocatalyst is characterized in that the NiFe-LDH sheets prepared by the electrodeposition method have certain mechanical strength, and the NiFe-LDH is in Cu2Se nano-wires are distributed in a crossed way, so that active sites are fully exposed, and OH is facilitated-The access of (b) also facilitates the escape of gaseous products.
(4) The core-shell Cu2Cu in Se @ NiFe-LDH electrocatalyst2The synergistic effect between Se and NiFe-LDH improves the charge transmission of the nickel-iron hydrotalcite nano-sheets, overcomes the defects of poor conductivity and easy aggregation of the single NiFe-LDH nano-sheets, and improves the catalytic performance of the composite structure.
Description of the drawings:
FIG. 1 shows Cu obtained in example 12Se and Cu2XRD diffractogram of Se @ NiFe-LDH sample.
FIG. 2 shows Cu obtained in example 12Scanning electron micrographs of Se samples.
FIG. 3 shows Cu obtained in example 12Scanning electron microscope photograph of Se @ NiFe-LDH sample.
FIG. 4 is a transmission electron micrograph of the sample obtained in example 1.
FIG. 5 is a high-resolution TEM image of the sample obtained in example 1.
FIG. 6 is an OER linear sweep voltammogram of four samples obtained in example 1, example 2, example 3, and example 4 in a 1mol/L KOH solution.
FIG. 7 is an OER linear sweep voltammogram of three samples obtained in example 1, example 5, and example 6 in a 1mol/L KOH solution.
FIG. 8 shows Cu obtained in example 12Se and Cu2OER linear sweep voltammograms of six samples of Se @ NiFe-LDH, example 7, example 8, example 9 and comparative example 1 in a 1mol/L KOH solution.
FIG. 9 shows Cu obtained in example 12Se@Ni2/3Fe1/3Graph of constant voltage I-t test at 1.45V (vs RHE) for an LDH/CF electrode in 1mol/L KOH electrolyte.
FIG. 10 shows Cu obtained in example 12Se@Ni2/3Fe1/3-a multistep chronopotentiometric diagram of the LDH/CF electrode in a 1mol/L KOH electrolyte.
FIG. 11 shows Cu obtained in example 12Se and Cu2Electrochemical impedance plots of six samples of Se @ NiFe-LDH, example 7, example 8, example 9, and comparative example 1 in a 1mol/L KOH solution.
FIG. 12 shows Cu obtained in example 12Se and Cu2Linear scanning voltammograms of HER in 1mol/L KOH solution for five samples obtained from Se @ NiFe-LDH samples, comparative example 1, comparative example 2 and comparative example 3.
FIG. 13 is an OER linear scanning voltammogram in a 1mol/L KOH solution when five samples obtained in example 1, example 2, comparative example 9, comparative example 10 and comparative example 11 were used as an electrolyzed water catalyst
The specific implementation mode is as follows:
for a further understanding of the invention, reference will now be made to the following examples and drawings, which are not intended to limit the invention in any way.
Example 1:
(1)Cu2preparation of Se/CF
Soaking commercial foam copper with the specification of 3cm multiplied by 4cm in a hydrochloric acid solution with the concentration of 37% for 10 minutes, and washing for a plurality of times by using deionized water and absolute ethyl alcohol; the cleaned copper foam is put into 80mLNaOH and (NH)4)2S2O8The mixed solution is soaked for 20min, so that light blue Cu (OH) grows on the surface in situ2Nanowire, taking out Cu (OH) grown thereon2Washing the foam copper of the nanowire with deionized water, and drying in an oven at 60 ℃ for 6 h; drying the Cu (OH)2Placing the nanowire in a tube furnace, simultaneously placing 0.1g selenium powder at the front end of the tube furnace, heating to 400 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, keeping for 30min, taking out a sample after the tube furnace is naturally cooled, and washing with deionized water and ethanol for several times to obtain Cu 2Se/CF, drying for later use;
(2)Cu2preparation of Se @ NiFe-LDH/CF
With Cu2Se/CF as working electrode, Pt wire electrode as counter electrode, saturated calomel electrode as reference electrode, and Ni (NO) as electrolyte3)2And FeSO4Mixed aqueous solution of (3), Ni (NO)3)2And FeSO4The concentration of the copper is 0.2M and 0.1M respectively, and the copper is electrified for 120s under the condition that the potential is minus 1.0V to carry out the electrodeposition reaction so as to grow NiFe-LDH on the surface of the copper, thus preparing the nuclear shell Cu2Se@Ni2/ 3Fe1/3LDH/CF catalyst.
Example 2:
(1)Cu2preparation of Se/CF
Reference was made to the procedure and conditions of step (1) in example 1.
(2)Cu2Preparation of Se @ NiFe-LDH/CF
Referring to the method and preparation conditions of step (2) in example 1, setting the electrodeposition time to 60s to obtain copper selenide @ ferronickel hydrotalcite nanosheet electrocatalyst, noted as Cu2Se@Ni2/3Fe1/3-LDH/CF-60；
Example 3:
(1)Cu2preparation of Se/CF
Reference was made to the procedure and conditions of step (1) in example 1.
(2)Cu2Preparation of Se @ NiFe-LDH/CF
Referring to the method and preparation conditions of step (2) in example 1, the electrodeposition time is set to 90s to obtain copper selenide @ ferronickel hydrotalcite nanosheet electrocatalyst, which is denoted as Cu2Se@Ni2/3Fe1/3-LDH/CF-90；
Example 4:
(1)Cu2preparation of Se/CF
Reference was made to the procedure and conditions of step (1) in example 1.
(2)Cu2Preparation of Se @ NiFe-LDH/CF
Referring to the method and preparation conditions of step (2) in example 1, the electrodeposition time is set to 150s to obtain copper selenide @ ferronickel hydrotalcite nanosheet electrocatalyst, which is denoted as Cu 2Se@Ni2/3Fe1/3-LDH/CF-150；
Example 5:
(1)Cu2preparation of Se/CF
Reference was made to the procedure and conditions of step (1) in example 1.
(2)Cu2Preparation of Se @ NiFe-LDH/CF
Referring to the method and preparation conditions of step (2) in example 1, only Ni (NO) in the electrolyte solution was added3)2And FeSO4The concentration of the copper selenide @ ferronickel hydrotalcite nanosheet electrocatalyst is changed to 0.2M and 0.05M respectively to obtain the copper selenide @ ferronickel hydrotalcite nanosheet electrocatalyst which is marked as Cu2Se@Ni2/3Fe1/3-LDH/CF-0.15；
Example 6:
(1)Cu2preparation of Se/CF
Reference was made to the procedure and conditions of step (1) in example 1.
(2)Cu2Preparation of Se @ NiFe-LDH/CF
Referring to the method and preparation conditions of step (2) in example 1, only Ni (NO) in the electrolyte solution was added3)2And FeSO4The concentration of the copper selenide @ ferronickel hydrotalcite nanosheet electrocatalyst is changed to 0.3M and 0.15M respectively to obtain the copper selenide @ ferronickel hydrotalcite nanosheet electrocatalyst which is marked as Cu2Se@Ni2/3Fe1/3-LDH/CF-0.45；
Example 7:
(1)Cu2preparation of Se/CF
Reference was made to the procedure and conditions of step (1) in example 1.
(2)Cu2Preparation of Se @ NiFe-LDH/CF
Referring to the method and preparation conditions of step (2) in example 1, only Ni (NO) in the electrolyte solution was added3)2And FeSO4The concentration of the copper selenide @ ferronickel hydrotalcite nanosheet electrocatalyst is respectively changed to 0.1M and 0.2M to obtain the copper selenide @ ferronickel hydrotalcite nanosheet electrocatalyst which is marked as Cu2Se@Ni2/3Fe1/3-LDH/CF-1:2；
Example 8:
(1)Cu2preparation of Se/CF
Reference was made to the procedure and conditions of step (1) in example 1.
(2)Cu2Preparation of Se @ NiFe-LDH/CF
Referring to the method and preparation conditions of step (2) in example 1, only Ni (NO) in the electrolyte solution was added3)2And FeSO4The concentration of the copper selenide @ ferronickel hydrotalcite nanosheet electrocatalyst is changed to 0.15M and 0.15M respectively to obtain the copper selenide @ ferronickel hydrotalcite nanosheet electrocatalyst which is marked as Cu2Se@Ni2/3Fe1/3-LDH/CF-1:1；
Example 9:
(1)Cu2preparation of Se/CF
Reference was made to the procedure and conditions of step (1) in example 1.
(2)Cu2Preparation of Se @ NiFe-LDH/CF
Referring to the method and preparation conditions of step (2) in example 1, only Ni (NO) in the electrolyte solution was added3)2And FeSO4The concentration of the copper selenide @ ferronickel hydrotalcite nanosheet electrocatalyst is respectively changed to 0.225M and 0.075M, so that the copper selenide @ ferronickel hydrotalcite nanosheet electrocatalyst is obtained and is marked as Cu2Se@Ni2/3Fe1/3-LDH/CF-3:1；
Comparative example 1:
referring to the method and preparation conditions in example 2, the only difference is that the nickel-iron hydrotalcite nanosheets, noted as Ni, are directly electrodeposited on the surface of the treated foamy copper2/3Fe1/3-LDH/CF；
Comparative example 2:
soaking commercial foam copper with the specification of 1cm multiplied by 2cm in a hydrochloric acid solution with the concentration of 37% for 10 minutes, and washing for a plurality of times by using deionized water and absolute ethyl alcohol; will be cleaned upThe copper foam of (2) was put into 80mL of NaOH and (NH)4)2S2O8The mixed solution is soaked for 20min, so that light blue Cu (OH) grows on the surface in situ2Nanowires, denoted Cu (OH)2NWs/CF；
Comparative example 3:
soaking commercial foam copper with the specification of 1cm multiplied by 2cm in a hydrochloric acid solution with the concentration of 37% for 10 minutes, and washing for a plurality of times by using deionized water and absolute ethyl alcohol, and marking as Cu foam;
FIG. 1 shows Cu obtained in example 12Se and Cu2XRD test pattern of Se @ NiFe-LDH sample. As can be seen from the figure, Cu2The Se catalyst has obvious characteristic peaks at 36.50 degrees, 42.69 degrees, 61.5 degrees and 73.69 degrees, is doped with a small amount of CuO, and shows diffraction peaks of 111, 200, 220 and 311 surfaces, which indicate that copper oxide exists in a sample. The catalyst has obvious characteristic peaks at 25.41 degrees and 43.91 degrees, corresponding to Cu 2222 and 504 planes of Se. Cu2Se@Ni2/3Fe1/3LDH samples in addition to CuO and Cu2Besides the characteristic peaks of Se, the characteristic peaks of 003, 006, 012, 015 and 018 planes of NiFe-LDH appear at 11.58 degrees, 23.33 degrees, 34.51 degrees, 39.59 degrees and 46.55 degrees, which proves that the core-shell copper selenide @ ferronickel hydrotalcite nanosheet electrocatalyst is successfully prepared.
FIG. 2 shows Cu obtained in example 12Scanning electron microscopy of Se nanowire samples. As can be seen from the figure, the nanowires are uniformly grown on the surface of the foam copper, the diameters of the nanowires are 150-250 nm, the shapes are regular, the sizes are uniform, the density is high, and the hydrotalcite deposition is facilitated. According to the literature, copper selenide has good electron transport capacity and certain oxygen evolution reaction catalytic activity, and is very beneficial to improving the catalytic activity of the catalyst OER.
FIG. 3 shows the core-shell Cu obtained in example 12Se@Ni2/3Fe1/3Scanning electron micrographs of LDH samples. As can be seen from the figure, the hydrotalcite nano-sheets are uniformly and alternately grown in Cu2On Se nano-wire, the ordered stereo structure greatly improves the specific surface area of the catalyst and is beneficial to OH-And release of gaseous productsAnd (4) placing. The thickness of the nano-sheet is less than 10nm, and the ultrathin structure is beneficial to the exposure of active sites and the improvement of electrocatalytic performance.
FIG. 4 shows core-shell Cu obtained in example 12Se@Ni2/3Fe1/3Transmission electron micrograph of LDH sample. As can be seen from the figure, NiFe-LDH nanosheets are in Cu2The length of the Se nanowire deposit is about 100-150 nm, the thickness of the nanosheet is less than 10nm, the nanosheet is uniformly distributed, and the appearance is good and is consistent with the scanning electron microscope image in figure 3.
FIG. 5 shows core-shell Cu obtained in example 12Se@Ni2/3Fe1/3High resolution transmission electron microscopy of LDH samples. From the figure, lattice fringes were clearly observed, the 0.25nm lattice fringe corresponding to the (012) crystal plane of NiFe-LDH, and the 0.34nm lattice fringe corresponding to Cu2Se (112) crystal face, and the existence of the several characteristic peaks proves that the NiFe-LDH nano-sheets are successfully deposited on Cu2Se surface.
FIG. 6 is an OER linear scan voltammogram of four samples from example 1, example 2, example 3, and example 4 in a 1mol/LKOH electrolyte, with comparative analysis of deposition time versus core-shell Cu 2Influence of Se @ NiFe-LDH electrocatalyst OER Activity, found at 50mA · cm-2Sample Cu obtained at a deposition time of 120 seconds at a current density of (1)2Se@Ni2/3Fe1/3The initial potential of LDH-120 is minimal and the catalyst has optimal catalytic activity.
FIG. 7 is an OER linear sweep voltammogram of three samples obtained in examples 1, 5 and 6 in a 1mol/L KOH electrolyte, comparing the total molar concentration of nickel iron ions in the deposition solution versus the core-shell Cu2The influence of the oxygen evolution reaction activity of the Se @ NiFe-LDH electrocatalyst is found to be 50mA · cm-2At a current density of 0.3M, Cu obtained at a total molar concentration of metal ions2Se@Ni2/3Fe1/3The initial potential of the-LDH-0.30 sample is the smallest, and the catalyst has the best catalytic activity.
FIG. 8 shows Cu obtained in example 12Se and Cu2Six samples of Se @ NiFe-LDH, example 7, example 8, example 9 and comparative example 1Linear scanning voltammogram of the product in 1mol/L KOH electrolyte. As can be seen from the figure, under the condition of ensuring that the concentration of the total metal ions in the ferronickel is not changed by 0.3M, only the proportion of the metal ferronickel ions is changed, and the proportion is 50 mA-cm-2At a current density of (2), Cu was obtained when the molar ratio of nickel to iron metal ions was 2:12Se@Ni2/3Fe1/3The LDH sample has the smallest initial potential and the largest gradient, so that the catalyst has the best catalytic activity in the proportion.
FIG. 9 shows Cu obtained in example 12Se@Ni2/3Fe1/3The time-current profile of the LDH electrocatalyst at a constant voltage of 1.45v (vs rhe) as shown, experienced 80 hours of testing with little apparent decrease in current density, indicating good long-term stability and durability of the catalyst.
FIG. 10 shows Cu obtained in example 12Se@Ni2/3Fe1/3Multistep chronopotentiometric plot of LDH electrocatalyst, current density from 100mA cm-2To 190mA cm-2The increase amplitude is 10 mA-cm every two hours-2There was substantially no change in current density during the first two hours, and the current density was relatively smooth with no significant fluctuations over the next twenty hours. This indicates that Cu2Se@Ni2/3Fe1/3the-LDH electrocatalyst has better catalytic activity and stability in the process of catalyzing OER.
FIG. 11 shows Cu obtained in example 1 of the present invention2Se and Cu2Electrochemical impedance spectra of Se @ NiFe-LDH, example 7, example 8, example 9 and comparative example 1 at different ratios of electrocatalyst open circuit potential of 1.48V (vs RHE) in 1mol/L KOH electrolyte, and electrochemical impedance of the catalyst was measured at open circuit potential in a stable 1mol/L KOH solution. As can be seen from the figure, Cu2Se@Ni2/3Fe1/3-LDH having a minimum charge transfer resistance, less than Cu for other metal proportions 2Se @ NiFe-LDH, also less than Cu2Se/CF and Ni2/3Fe1/3LDH/CF. This indicates that Cu2Se@Ni2/3Fe1/3Kinetic Process of LDH in comparison with other catalystsAnd is faster.
FIG. 12 shows Cu obtained in example 1 of the present invention2Se and Cu2HER linear sweep voltammograms of Se @ NiFe-LDH, comparative example 1, comparative example 2 and comparative example 3 in different proportions of the obtained electrocatalysts in a 1mol/L KOH electrolyte as shown in the figure, in which the Cu is present2Se@Ni2/3Fe1/3LDH electrocatalyst at 10mA cm-2The initial potential is minimum and the catalytic activity is optimal. Although the initial potential is smaller than that of a commercial Pt/C electrode, the Pt/C electrode has good application potential under high current density.
FIG. 13 shows Cu obtained in example 12Se and Cu2Scanning voltammogram of five samples obtained from Se @ NiFe-LDH, comparative example 1, comparative example 2 and comparative example 3 for fully electrolyzed water under a two-electrode system, in which five electrocatalysts, Cu2Se@Ni2/3Fe1/3the-LDH has the minimum initial potential and the highest catalytic activity, and is a bifunctional electrocatalyst with great application prospect.
The electrocatalytic performance test adopts a saturated calomel electrode as a reference electrode, a Pt electrode as a counter electrode, the sweeping speed is 5mV/s, the electrolyte is 1mol/LKOH electrolyte, all potentials are converted into reversible hydrogen potential (RHE), and the conversion formula is 
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (4)
1. The core-shell copper selenide @ nickel iron hydrotalcite electrocatalyst is characterized in that the catalyst takes foam copper as a substrate, and Cu (OH) grows in situ on the surface of the catalyst in an alkaline medium through a chemical oxidation method2Selenizing the nano-wire with selenium powder in a tube furnace to obtain copper selenide nano-wire, and growing nickel-iron hydrotalcite on the surface by electrodeposition(ii) a Copper foam is designated CF and copper selenide is designated Cu2Se, nickel-iron hydrotalcite is recorded as NiFe-LDH, and copper selenide @ nickel-iron hydrotalcite is recorded as Cu2Se@NiFe-LDH；
The preparation method of the core-shell copper selenide @ ferronickel hydrotalcite electrocatalyst is characterized by comprising the following steps of:
(1) Cu2preparation of Se/CF
Soaking commercial foam copper with the specification of 3 cm multiplied by 4 cm in a hydrochloric acid solution with the concentration of 37% for 10 minutes, and washing for a plurality of times by using deionized water and absolute ethyl alcohol; the cleaned foamy copper is put into 80 mL NaOH and (NH)4)2S2O8The mixed solution is soaked for 20 min, so that light blue Cu (OH) grows on the surface in situ 2Nanowire, taking out Cu (OH) grown thereon2Washing the foam copper of the nanowire with deionized water, and drying in an oven at 60 ℃ for 6 h; drying the Cu (OH)2Placing the nanowire in a tube furnace, simultaneously placing 0.1 g selenium powder at the front end of the tube furnace, heating to 400 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere, keeping for 30 min, taking out a sample after the tube furnace is naturally cooled, and washing with deionized water and ethanol for several times to obtain Cu2Se/CF, drying for later use;
(2) Cu2preparation of Se @ NiFe-LDH/CF
With Cu2Se/CF as working electrode, Pt wire electrode as counter electrode, saturated calomel electrode as reference electrode, and Ni (NO) as electrolyte3)2And FeSO4Electrifying the mixed aqueous solution for 60-150 s under the condition that the potential is-1.0V to perform an electrodeposition reaction so as to grow NiFe-LDH on the surface of the mixed aqueous solution, and preparing the nuclear shell Cu2Se @ NiFe-LDH/CF catalyst.
2. The core-shell copper selenide @ ferronickel hydrotalcite-like electrocatalyst according to claim 1, wherein in step (1) of the preparation method, NaOH and (NH)4)2S2O8NaOH and (NH)4)2S2O8The molar concentrations of the compounds are respectively 2.5 and 0.125 mol/L; ni (NO) in step (2)3)2And FeSO4The total concentration of metal ions in the mixed aqueous solution is 0.15-0.45 mol/L, Ni (NO)3)2And FeSO 41-6: 2.
3. the core-shell copper selenide @ ferronickel hydrotalcite electrocatalyst according to claim 1, characterized in that the catalyst is in a nanowire shape, and the diameter of the catalyst is 150-250 nm; with Cu2Se is used as a core, NiFe-LDH sheets are used as shells, and the thickness of the NiFe-LDH sheets is less than 10 nm.
4. The core-shell copper selenide @ ferronickel hydrotalcite electrocatalyst according to any one of claims 1 to 3, wherein the electrocatalyst is used for an alkaline electrolysis water anodic oxygen evolution reaction.
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