CN111939947A - Preparation method of nanosheet array electrocatalyst - Google Patents
Preparation method of nanosheet array electrocatalyst Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 19
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- 239000003054 catalyst Substances 0.000 description 5
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- B01J35/33—
-
- 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
-
- 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 relates to a preparation method of a nanosheet array electrocatalyst, in particular to a preparation method of a NiCoSe mesoporous nanosheet array @ NF electrocatalyst with excellent electrochemical properties. In the invention, C is used4H6N2、Co(NO3)2·6H2O、C2H6O, selenium powder, NaOH and N2H4·H2The experimental method for preparing the NiCoSe @ NF nanosheet array by taking O as a main raw material is characterized by comprising the following steps of: firstly, synthesizing a ZIF-67@ NF nanosheet array, then obtaining a NiCo LDH nanosheet array @ NF with a mesoporous structure by ion exchange in a water and ethanol solution, and finally selenizing at 180 ℃ for 12h to realize the preparation of a final target product.
Description
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to a preparation method of a nanosheet array electrocatalyst.
Background
Electrochemical water splitting is considered to be one of the most attractive and sustainable methods for efficient renewable energy production and conversion. The decomposition of water is divided into two half-reactions, the Hydrogen Evolution Reaction (HER) and the Oxygen Evolution Reaction (OER). To facilitate these two reactions, noble metal compounds are the most advanced catalysts at present, such as Pt, Pd for HER and IrO for OER2、RuO2And the like. However, their poor stability and high price limit their use in large quantities in industry. In order to solve this problem, intensive research has been conducted on non-noble metal electrocatalysts such as transition metal selenides, phosphides, sulfides, carbons, and alloys. However, in practice, the cathode and anode should operate in the same electrolyte to maintain overall water splitting. Thus, there is a need for stable bifunctional electrocatalysts that catalyze both HER and OER in the same electrolyte. Metal selenides have a distinct crystal structure and rich chemical valence states and have recently proven to be promising catalysts. Theoretical studies have shown that incorporation of transition metal atoms into Ni-based catalysts can improve their electrochemical properties. Despite some advances, there have been few reports of studies on the water splitting reaction of binary metal selenides. Therefore, it is necessary to greatly improve the electrocatalytic performance by regulating the composition and the nanostructure of the electrocatalytic catalyst. The active sites and conductivity of the electrocatalyst are the effectsAn important factor affecting the water splitting performance. .
Disclosure of Invention
The invention aims to provide a preparation method of a nano material which can be applied to the field of electrocatalysis, and the nano material prepared by the method has excellent electrochemical performance, simple preparation process and easy realization of industrialization.
In order to achieve the above object, the present invention provides a method for preparing a nanosheet array electrocatalyst, comprising the steps of:
1) preparing a nanosheet array ZIF-67@ NF: mixing 2-methylimidazole aqueous solution with Co (NO)3)2·6H2Mixing and stirring the O aqueous solution according to the volume ratio of 1:1, soaking the pretreated foamed nickel in the mixed solution for reaction, removing the liquid, washing and drying to obtain a nanosheet array ZIF-67@ NF;
2) preparation of a nanosheet array NiCo LDH @ NF: placing the nanosheet array ZIF-67@ NF prepared in the step 1) in an ethanol water solution, heating for reaction, removing liquid, washing and drying to obtain a nanosheet array NiCo LDH @ NF;
3) preparation of a nanosheet array NiCoSe @ NF: mixing selenium powder-hydrazine hydrate solution with 1.6mol/L NaOH aqueous solution according to the volume ratio of 1: 2; placing the NiCo LDH @ NF in the step 2) into a solution, heating for reaction, naturally cooling, washing and drying to obtain the nanosheet array NiCoSe @ NF.
Wherein, in the step 1), the concentration of the 2-methylimidazole aqueous solution is 32.48g/L (0.4 mol/L); co (NO)3)2·6H2The concentration of the O solution was 14.55g/L (0.05 mol/L).
Wherein in the step 1), the stirring time is 5 min; the soaking time is 4 h; the washing method comprises the steps of washing for multiple times by using deionized water and absolute ethyl alcohol; the drying condition is drying for 6h at 60 ℃.
The pretreatment method of the foamed nickel comprises the steps of ultrasonically cleaning the foamed nickel for 20 minutes by respectively using 3.0M hydrochloric acid, acetone and water, then washing by using absolute ethyl alcohol, and drying the washed foamed nickel for 6 hours at 60 ℃ to obtain the pretreated foamed nickel.
Wherein, in the step 2), the ethanol aqueous solution is 90% by volume; the heating temperature is 90 ℃, the heating time is 2h, and the drying condition is 60 ℃ for 6 h.
In the step 3), the concentration of selenium powder in the selenium powder-hydrazine hydrate solution is 0.2-2 mol/L; the concentration of the NaOH aqueous solution was 1.6 mol/L.
Wherein, in the step 3), the concentration of the selenium powder in the selenium powder-hydrazine hydrate solution is 0.4mol/L
Wherein the selenium powder is mixed with Co (NO)3)2·6H2The molar ratio of O is 1-10: 2
Wherein the selenium powder is mixed with Co (NO)3)2·6H2The molar ratio of O is 1:1
Wherein in the step 3), the heating temperature is 180 ℃; the heating reaction time is 12 h; the washing method comprises the steps of washing for multiple times by using deionized water and absolute ethyl alcohol; the drying condition is drying for 6h at 60 ℃. .
The invention has the beneficial effects that: the invention adopts a two-step hydrothermal method to synthesize the NiCoSe @ NF nanosheet array, and prepares the nanomaterial with excellent electrochemical properties. The invention overcomes the defect that the nickel foam becomes brittle by selenization (under the condition of no addition of NaOH, the nickel foam loses toughness and cannot be mechanically cut) by adjusting the pH value in the selenization process. The method has the advantages of simple operation, environmental protection, economy, convenience and the like, and is easy to realize large-scale production.
Drawings
FIG. 1 is a process flow diagram of a preparation method of a target product NiCoSe @ NF nanosheet array of the invention.
FIG. 2 is a scanning diagram of an NiCoSe @ NF nanosheet array as a target product of the present invention.
FIG. 3 is an X-ray diffraction pattern of an NiCoSe @ NF nanosheet array of the target product of the present invention.
FIG. 4 is an electrochemical property diagram of an NiCoSe @ NF nanosheet array, which is a target product of the present invention, wherein the diagram A is a hydrogen production linear scanning voltammetry curve with working electrodes NiCoSe @ NF1, NiCoSe @ NF2, NiCoSe @ NF3, NiCoSe @ NF4, NiCoSe @ NF5, NiCoSe @ NF6, NF, NiCoLDH @ NF and Pt/C @ NF, respectively, and the diagram B is a diagram with working electrodes NiCoSe @ NF1, NiCoSe @ NF2, NiCoSe @ NF3, NiCoSe @ NF4, NiCoSe NF5 and NiC @ NF, respectivelyoSe @ NF6, NF, NiCo LDH @ NF, and IrO2The graph C shows that the working electrode is NiCoSe @ NF1| | NiCoSe @ NF1, NiCoSe @ NF2| | NiCoSe @ NF2, NiCoSe @ NF3| | NiCoSe @ NF3, NiCoSe @ NF4| | NiCoSe @ NF4, NiCoSe @ NF6| | | NiCoSe @ NF6, LDH @ NF | | NiCo LDH @ NF, NF | | | NF and IrO2@ NF (+) | Pt/C @ NF (-) full-resolution linear sweep voltammogram.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
The raw material reagents mentioned in the following examples can be ordered from the alatin reagent official website, specifically: dimethylimidazole (C)4H6N2Avastin reagent) as analytical grade; cobalt nitrate (Co (NO)3)2·6H2O, alatin reagent) as analytical grade; sodium hydroxide (NaOH, alatin reagent) was analytically pure; hydrazine hydrate (N)2H4·H2O, alatin reagent) as analytical grade; selenium powder (Se, an alatin reagent) is analytically pure; ethanol (C)2H6O, avadin reagent) was analytical grade.
The invention adopts 2-methylimidazole (C)4H6N2) Cobalt nitrate hexahydrate (Co (NO)3)2·6H2O), ethanol (C)2H6O), selenium powder, NaOH and hydrazine hydrate (N)2H4·H2O) is used as a main raw material, a NiCoSe @ NF nanosheet array is prepared, a ZIF-67@ NF nanosheet array is firstly synthesized and successfully converted into NiCo LDH @ NF, and then selenylation is carried out for 12 hours at 180 ℃ to realize the preparation of a final target product.
Example 1
The preparation method of the nanosheet array NiCoSe @ NF1 comprises the following steps:
1) preparing a nanosheet array ZIF-67@ NF:
11) and (3) pretreating the foamed nickel, namely cleaning the foamed nickel before use, performing ultrasonic treatment on the foamed nickel by using 3.0M hydrochloric acid, acetone and water for 20 minutes respectively, washing the foamed nickel for multiple times by using absolute ethyl alcohol, and drying the washed foamed nickel for 6 hours at the temperature of 60 ℃ to obtain the pretreated foamed nickel.
12) 1.3136g of 2-methylimidazole and 0.582g of cobalt nitrate hexahydrate (corresponding to a molar number of 0.2mmol) were respectively dispersed in 40ml of deionized water, and after magnetic stirring for 10min, 2-methylimidazole was rapidly poured into Co (NO)3)2·6H2In the O solution, the transparent solution quickly turns into blue-purple, and the stirring is continued for 5 min.
13) A block of 2 x 4cm-2The foam nickel is put into the nano-sheet array ZIF-67@ NF, and is kept stand for 4 hours, washed for a plurality of times by using deionized water and absolute ethyl alcohol, and dried for 6 hours at the temperature of 60 ℃ to obtain the nano-sheet array ZIF-67@ NF.
2) Preparation of a nanosheet array NiCo LDH @ NF: putting the ZIF-67@ NF prepared in the step 1 into 100ml of ethanol water solution, keeping the temperature at 90 ℃ for 2h, washing the solution for a plurality of times by using deionized water and absolute ethyl alcohol, and drying the solution at 60 ℃ for 6h to obtain NiCo LDH @ NF; wherein the volume ratio of the ethanol water solution is ethanol: water 90: 10.
3) Preparation of a nanosheet array NiCoSe @ NF: 1 millimole of selenium powder was dissolved in 5ml of hydrazine hydrate (N)2H4·H2O), dissolving 16mmol of NaOH in 10ml of deionized water, respectively magnetically stirring for 10min, pouring the aqueous solution of NaOH into a Se powder hydrazine hydrate solution, and stirring for 3h to obtain a mixed solution. And (3) placing the NiCo LDH @ NF nanosheets into the mixed solution, keeping the mixed solution at 180 ℃ for 12h, naturally cooling, washing for a plurality of times by using deionized water and absolute ethyl alcohol, and drying at 60 ℃ for 6h to obtain the nanosheet array NiCoSe @ NF 1.
Example 2
Preparation of the nanosheet array NiCoSe @ NF2, the using amount of the selenium powder in the step 3) in the embodiment 1 is changed into 2 millimole of selenium powder, and the using amounts of other steps and components are not changed, so that the nanosheet array NiCoSe @ NF2 is obtained.
Preparation of the nanosheet array NiCoSe @ NF3, the using amount of the selenium powder in the step 3) in the embodiment 1 is changed into 4 millimole of selenium powder, and the using amounts of other steps and components are not changed, so that the nanosheet array NiCoSe @ NF3 is obtained.
Preparation of the nanosheet array NiCoSe @ NF4, the using amount of the selenium powder in the step 3) in the embodiment 1 is changed into 6 millimole of selenium powder, and the using amounts of other steps and components are not changed, so that the nanosheet array NiCoSe @ NF4 is obtained.
In the preparation of the nanosheet array NiCoSe @ NF5, the using amount of the selenium powder in the step 3) in the embodiment 1 is changed into 8 millimole of selenium powder, and the using amounts of other steps and components are not changed, so that the nanosheet array NiCoSe @ NF5 is obtained.
Preparation of the nanosheet array NiCoSe @ NF6, the using amount of the selenium powder in the step 3) in the embodiment 1 is changed into 10 millimole of selenium powder, and the using amounts of other steps and components are not changed, so that the nanosheet array NiCoSe @ NF6 is obtained.
Note that the amount of hydrazine hydrate is 5ml in the reaction process, and a small amount of hydrazine hydrate can lead to incomplete dissolution of selenium powder, thus leading to incomplete selenization reaction; NaOH is required to be added to adjust the pH value of the solution in the reaction process, and in the reaction without adding NaOH, the foamed nickel loses toughness and cannot be mechanically cut.
Example 3 Performance testing
1. Scanning electron microscope characterization is carried out on the nanosheet array NiCoSe @ NF2, and Field Emission Scanning Electron Microscope (FESEM) image analysis is carried out on a JEOLJ SM-7800F with the voltage of 10.0kV, and the result is shown in FIG. 2. As can be seen from FIG. 2, NiCoSe nanosheets with uniform sizes grow on the surface of the foamed nickel, and are thinner than precursor nanosheets, so that the electrolyte solution can penetrate through the nanosheets more easily, and the electrochemical properties can be improved.
2. X-ray diffraction of the nanosheet array NiCoSe @ NF2 using a Cu target radiation source of a Mac scientific MXP-18X-ray diffractometer is shown in FIG. 3. FIG. 3 is an X-ray diffraction pattern of a nanosheet array NiCoSe @ NF2 of the present invention. As can be seen from the figure, the target product contains diffraction peaks of NiSe, CoSe and Ni at the same time, which indicates the successful synthesis of the target product.
3. Electrochemical property detection
In a standard three-electrode system, the electrolyte is 1M KOH, and HER/OER electrochemical performance tests were performed at ambient temperature using a CHI760E electrochemical workstation (shanghai chenhua corporation), in which a graphite rod was used as a counter electrode and a Hg/HgO electrode was used as a reference electrode, and prepared samples NiCoSe @ NF1, NiCoSe @ NF2, NiCoSe @ NF3, NiCoSe @ NF4, NiCoSe @ NF5, and NiCoSe @ NF6 (at a catalyst loading of 4.2mg cm)-2Lower cut into 0.3X 0.3cm2) As working electrode, electrochemical performance test was performedMeasuring, simultaneously, NF, NiCo LDH, IrO2The same test was carried out with @ NF and Pt/C as working electrodes as comparative data, and the results are shown in FIG. 4. FIG. 4 is an electrochemical property diagram of a nanosheet array NiCoSe @ NF1-6 of the present invention, wherein FIG. A is a hydrogen production linear scan voltammetry curve with working electrodes NiCoSe @ NF1, NiCoSe @ NF2, NiCoSe @ NF3, NiCoSe @ NF4, NiCoSe @ NF5, NiCoSe @ NF6, NF, NiCo LDH @ NF and Pt/C @ NF, respectively, and FIG. B is a hydrogen production linear scan voltammetry curve with working electrodes NiCoSe @ NF1, NiCoSe @ NF2, NiCoSe @ NF3, NiCoSe @ NF4, NiCoSe @ NF5, NiCoSe @ NF6, NF, NiCo LDH @ NF and IrO @ NF, respectively2The graph C shows that the working electrode is NiCoSe @ NF1| | NiCoSe @ NF1, NiCoSe @ NF2| | NiCoSe @ NF2, NiCoSe @ NF3| | NiCoSe @ NF3, NiCoSe @ NF4| | NiCoSe @ NF4, NiCoSe @ NF6| | | NiCoSe @ NF6, LDH @ NF | | NiCo LDH @ NF, NF | | | NF and IrO2@ NF (+) | Pt/C @ NF (-) full-resolution linear sweep voltammogram.
As can be seen from the figure, the nanosheet array NiCoSe @ NF5 has the most excellent HER performance among the six samples, at a current density of 10mAcm-2Overpotential was 170mV (FIG. 4A); the nanosheet array NiCoSe @ NF2 has the most excellent OER performance and the current density of 20mAcm-2When the overpotential is 278mV (FIG. 4B); in a full-hydrolytic test, a nanosheet array NiCoSe @ NF2 is used as an anode, and a nanosheet array NiCoSe @ NF5 is used as a cathode, so that the voltage value of the full-hydrolytic test is 1.51V (fig. 4C).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of the nanosheet array electrocatalyst is characterized by comprising the following steps of:
1) preparing a nanosheet array ZIF-67@ NF: mixing 2-methylimidazole aqueous solution with Co (NO)3)2·6H2Mixing and stirring the O aqueous solution according to the volume ratio of 1:1, soaking the pretreated foamed nickel in the mixed solution for reaction, removing the liquid, washing and drying to obtain a nanosheet array ZIF-67@ NF;
2) preparation of a nanosheet array NiCo LDH @ NF: placing the nanosheet array ZIF-67@ NF prepared in the step 1) in an ethanol water solution, heating for reaction, removing liquid, washing and drying to obtain a nanosheet array NiCo LDH @ NF;
3) preparation of a nanosheet array NiCoSe @ NF: mixing selenium powder-hydrazine hydrate solution with 1.6mol/L NaOH aqueous solution according to the volume ratio of 1: 2; placing the NiCo LDH @ NF in the step 2) into a solution, heating for reaction, naturally cooling, washing and drying to obtain the nanosheet array NiCoSe @ NF.
2. A method for preparing a nanosheet array electrocatalyst according to claim 1, wherein in step 1), the concentration of the aqueous 2-methylimidazole solution is 32.48 g/L; co (NO)3)2·6H2The concentration of the O solution was 14.55 g/L.
3. A method for preparing a nanosheet array electrocatalyst according to claim 1, wherein in step 1), the stirring time is 5 min; the soaking time is 4 h; the washing method comprises the steps of washing for multiple times by using deionized water and absolute ethyl alcohol; the drying condition is drying for 6h at 60 ℃.
4. A preparation method of a nanosheet array electrocatalyst according to claim 1, wherein the pretreatment method of the foamed nickel comprises ultrasonic cleaning of the foamed nickel with 3.0M hydrochloric acid, acetone and water for 20 minutes respectively, then rinsing with absolute ethanol, and drying the rinsed foamed nickel at 60 ℃ for 6 hours to obtain the pretreated foamed nickel.
5. A method for preparing a nanosheet array electrocatalyst according to claim 1, wherein in step 2), the aqueous ethanol solution is an aqueous ethanol solution having a volume fraction of 90%; the heating temperature is 90 ℃, the heating time is 2h, and the drying condition is 60 ℃ for 6 h.
6. The preparation method of a nanosheet array electrocatalyst according to claim 1, wherein in step 3), the concentration of selenium powder in the selenium powder-hydrazine hydrate solution is 0.2-2 mol/L; the concentration of the NaOH aqueous solution was 1.6 mol/L.
7. A preparation method of a nanosheet array electrocatalyst according to claim 6, wherein in step 3), the concentration of selenium powder in the selenium powder-hydrazine hydrate solution is 0.4 mol/L.
8. A process for the preparation of an electrocatalyst with nanoplate array according to any one of claims 1 to 7 wherein the selenium powder is mixed with Co (NO)3)2·6H2The molar ratio of O is 1-10: 2.
9. A method of preparing a nanosheet array electrocatalyst as claimed in claim 8, wherein the selenium powder is admixed with Co (NO)3)2·6H2The molar ratio of O is 1: 1.
10. A method for preparing a nanosheet array electrocatalyst according to claim 1, wherein in step 3), the heating temperature is 180 ℃; the heating reaction time is 12 h; the washing method comprises the steps of washing for multiple times by using deionized water and absolute ethyl alcohol; the drying condition is drying for 6h at 60 ℃.
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