CN109529849B - Method for synthesizing nickel-iron hydrotalcite nano array composite structure by in-situ self-sacrifice template and application - Google Patents
Method for synthesizing nickel-iron hydrotalcite nano array composite structure by in-situ self-sacrifice template and application Download PDFInfo
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- CN109529849B CN109529849B CN201811547839.1A CN201811547839A CN109529849B CN 109529849 B CN109529849 B CN 109529849B CN 201811547839 A CN201811547839 A CN 201811547839A CN 109529849 B CN109529849 B CN 109529849B
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- 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 title claims abstract description 50
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 48
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000001301 oxygen Substances 0.000 claims abstract description 36
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000012360 testing method Methods 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 229910000863 Ferronickel Inorganic materials 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000020477 pH reduction Effects 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000007809 chemical reaction catalyst Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910003271 Ni-Fe Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- B01J35/33—
-
- B01J35/61—
-
- 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
- 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
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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 belongs to the technical field of material science and electrocatalysis, and particularly relates to a method for synthesizing a nickel-iron hydrotalcite nano array composite structure by using an in-situ self-sacrificial template. The method takes a nickel-iron alloy sheet as an electrode substrate and a reaction template, grows a nickel-iron hydrotalcite nano array composite structure on the nickel-iron alloy sheet as an electrolytic water oxygen evolution reaction catalyst by an in-situ self-sacrifice template method, places the nickel-iron alloy sheet with the nickel-iron hydrotalcite nano array composite structure in an electrochemical three-electrode test system, and takes an electrolytic water oxygen evolution electrode in an alkaline medium, so that the electrolytic water oxygen evolution reaction can be efficiently carried out under a lower external voltage, and the nickel-iron hydrotalcite nano array composite structure has good stability. The preparation process is simple, the needed raw materials are cheap and have wide sources, the cost is saved, the industrial production is facilitated, and the preparation method has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of material science and electrocatalysis, and particularly relates to a method for synthesizing a nickel-iron hydrotalcite nano-array composite structure by using an in-situ self-sacrificial template, and a product and application thereof.
Background
Due to the limited fossil energy reserves and environmental pollution caused by combustion, the energy problem becomes a great problem to be solved urgently in human society. Electrocatalytic water splitting provides a sustainable strategy to provide clean energy through cathodic hydrogen evolution reactions and anodic oxygen evolution reactions. For the electrolytic water oxygen evolution reaction, an effective catalyst is essential because of the kinetic disadvantage of multiple steps of proton coupled electron transfer. Noble metal oxides, such as ruthenium dioxide and iridium dioxide, have heretofore exhibited high performance in catalysis of electrolytic water-out oxygen reactions. However, the high price and scarcity of these precious metals severely hamper their practical use. Therefore, development of a new catalyst having low price and excellent performance is urgently required.
Layered double hydroxides, also known as hydrotalcites, are composed of layers of divalent and trivalent metal cations coordinated by hydroxide anions. It has been extensively studied in the fields of catalysts, flame retardants, biomaterials, and the like. In recent years, their use as electroactive materials in supercapacitors and fuel cells has attracted considerable attention. To develop new catalysts with low price and excellent performance as alternatives to traditional electrolytic water oxygen evolution reaction catalysts should be key to the development of practical applications for many energy storage and conversion processes, including water splitting and metal air batteries.
Among the hydrotalcite structures, the hydrotalcite structure formed by nickel and iron and the derivatives thereof have extremely high catalytic activity for electrolytic water-to-oxygen evolution reaction, and are considered to be the most likely electrocatalyst for replacing noble metals. However, in practical applications, hydrotalcite materials also have the disadvantages of small specific surface area, poor electrical conductivity, easy aggregation, poor stability, etc. In order to overcome the above disadvantages, researchers often insert some carbon materials such as Graphene (GR) and Carbon Nanotube (CNT) between hydrotalcite layers, which can increase the conductivity of the composite material on one hand and prevent hydrotalcite from aggregating on the other hand, thereby improving its stability (for example, chinese patent CN 201510964020.5); the Chinese patent CN201610887588.6 adopts a microwave heating condensation reflux mode to prepare the nickel-iron hydrotalcite structure nanosheet, and has the structural morphology characteristics of ultrathin and large area; chinese patent 201610565736.2 discloses an integrated oxyhydroxide-ferronickel hydrotalcite oxygen evolution electrode with high catalytic activity and stability; in addition, a high-temperature exercise method and an electrodeposition method are also commonly used in the prior art for synthesizing the nickel-iron hydrotalcite material.
However, the synthesis method of the materials reported at the present stage has limitations, complex process, high cost, large energy consumption and the like; in addition, the prepared electrocatalyst is usually required to be loaded on a glassy carbon electrode or a two-dimensional substrate by methods such as drop coating and spray coating, and the methods require additional addition of a binder, so that the poor bonding, poor contact and uneven dispersion of the catalyst on the surface of the electrode can cause the obstruction of charge transmission, and the catalytic activity and stability of the electrode are seriously affected.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for synthesizing a nickel-iron hydrotalcite nano-array composite structure by in-situ self-sacrifice template.
Therefore, one of the objectives of the present invention is to provide a method for synthesizing a nickel iron hydrotalcite nano array composite structure in situ from a sacrificial template, which comprises the following specific operations:
a) pretreating a nickel-iron alloy sheet: repeatedly washing the nickel-iron alloy sheet with water and ethanol to remove surface impurities, placing the nickel-iron alloy sheet in absolute ethanol for ultrasonic treatment for 1-5 minutes, taking out the nickel-iron alloy sheet, and repeatedly washing the nickel-iron alloy sheet with ultrapure water; then ultrasonic acidification activation is carried out in 1mol/L hydrochloric acid for 1-6 minutes, and the product is taken out and repeatedly washed by ultrapure water; then placing the mixture in an oven at 60-80 ℃ to dry for 60-80 minutes;
b) preparation of reaction solution: taking a mixed solution of 5-25 ml of water and 25-5 ml of methanol as a solvent, adding 0.5-0.8 g of hexadecyl trimethyl ammonium bromide and 0.01-0.02 g of potassium hydroxide into the solvent, and stirring at normal temperature until the hexadecyl trimethyl ammonium bromide and the potassium hydroxide are completely dissolved to obtain a reaction solution;
c) placing the nickel-iron alloy sheet dried in the step a) into a 40 ml polytetrafluoroethylene lining, pouring the reaction solution obtained in the step b) into the lining, placing the lining into a 120-plus 180 ℃ drying oven after the reaction kettle is assembled, and carrying out hydrothermal reaction for 4-8 hours;
d) and taking the reaction kettle out of the oven, obtaining a nickel-iron alloy sheet from the polytetrafluoroethylene lining, repeatedly washing the nickel-iron alloy sheet with water and ethanol, drying at room temperature, and growing on the surface of the nickel-iron alloy sheet to obtain the nickel-iron hydrotalcite nano array composite structure.
In the step a), the nickel-iron alloy sheet is pretreated preferably by carrying out ultrasonic treatment on absolute ethyl alcohol for 3 minutes, carrying out ultrasonic acidification and activation on 1mol/L hydrochloric acid for 3-5 minutes, repeatedly washing with ultrapure water, and then drying in an oven at 80 ℃ for 60 minutes.
Among them, in the step b), it is preferable that a mixed solution of 5 ml of water and 25 ml of methanol is used as a solvent, the amount of the surfactant cetyltrimethylammonium bromide is 0.6 g, and 0.0168 g of potassium hydroxide is added to create an alkaline atmosphere.
Wherein, in the step c), the reaction kettle is arranged in an oven and undergoes hydrothermal reaction for 6 to 8 hours at the high temperature of 160-.
In the invention, the iron content of the ferronickel alloy sheet before pretreatment is 30%, 50% and 70%; preferably, the iron content of the ferronickel alloy sheet is 70%. The size of the nickel-iron alloy sheet is preferably 3 x 2cm2。
In the present invention, the repeated rinsing is generally 4 to 6 times.
The second purpose of the invention is to provide a nickel iron hydrotalcite nano array composite structure prepared by the method, which has a three-dimensional acicular nano array structure.
The invention also aims to provide the application of the nickel-iron hydrotalcite nano-array composite structure as the catalyst for the electrolytic water oxygen evolution reaction, which can obviously reduce the overpotential of the oxygen evolution reaction, has good stability, shows excellent catalytic activity of the electrolytic water oxygen evolution reaction and has good application prospect.
The invention also aims to provide an electrolytic water oxygen evolution electrode, wherein the nickel-iron alloy sheet with the grown nickel-iron hydrotalcite nano array composite structure is placed in an electrochemical three-electrode test system to be used as an electrolytic water oxygen evolution electrode, so that the electrolytic water oxygen evolution reaction can be efficiently carried out under a lower applied voltage in an alkaline medium, and the electrolytic water oxygen evolution electrode has good stability.
In the invention, the nickel-iron alloy sheet is pretreated to be acidified and activated, and the surface of the nickel-iron alloy sheet is rich in divalent nickel ions and trivalent iron ions. In the hydrothermal reaction process, methanol in the reaction solution serves as a reducing agent to reduce ferric ions into ferrous ions, and the ferrous ions play a key role in anchoring divalent nickel ions in the catalysis process; the surfactant cetyl trimethyl ammonium bromide in the reaction solution can effectively control the morphology of the nickel iron hydrotalcite nano array composite structure. The ferronickel alloy sheet of the reaction template is a three-dimensional pore channel structure, and a ferronickel hydrotalcite nano array composite structure synthesized in situ from the sacrificial template is used as an electrolytic water oxygen evolution reaction catalyst to form a three-dimensional needle-like nano array structure with a large specific surface area on the basis of the reaction template, so that catalytic active sites of the catalyst are greatly increased; meanwhile, the nickel-iron hydrotalcite nano array composite structure synthesized by the in-situ self-sacrifice template can be tightly combined with and well contacted with a nickel-iron alloy sheet serving as an electrode material, the nickel-iron alloy sheet growing with the nickel-iron hydrotalcite nano array composite structure is placed in an electrochemical three-electrode test system to serve as an electrolytic water oxygen evolution electrode, the electrolytic water oxygen evolution reaction can be efficiently carried out under a lower applied voltage in an alkaline medium, and the nickel-iron hydrotalcite nano array composite structure has good stability.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the invention utilizes the method of in-situ self-sacrifice template to synthesize the nickel-iron hydrotalcite nano-array composite structure as the catalyst for the electrolytic water oxygen evolution reaction, so that the catalyst and the electrode material can be tightly combined, thereby not only solving the problem of poor conductivity of hydroxide, but also promoting charge transmission.
2. The three-dimensional needle-like nano array structure with larger specific surface area is synthesized in situ by utilizing the three-dimensional pore structure of the reaction template, and the catalytic active sites of the catalyst are greatly increased, so that the oxygen evolution electrode can be used for efficiently carrying out the catalytic electrolysis water oxygen evolution reaction under lower applied voltage, and has good stability.
3. The synthesis process is simple, fast and easy to control, no additional salt source (nickel salt and iron salt) and no additional binder are needed, and the needed raw materials are wide in source and low in price.
4. The invention saves energy consumption and improves efficiency for the electrolytic water oxygen evolution reaction, has obvious effect, is suitable for large-scale industrial production and has good application prospect.
Drawings
FIG. 1 is a scanning electron microscope image of a substrate of a nickel-iron alloy sheet;
FIG. 2 is a scanning electron microscope image of the nickel iron hydrotalcite nano-array composite structure synthesized by the in-situ self-sacrifice template method in example 1;
FIG. 3 is a transmission electron microscope image of the nickel iron hydrotalcite nano-array composite structure synthesized by the in-situ self-sacrifice template method of example 1;
FIG. 4 is a diagram of a nickel iron hydrotalcite nano-array composite structure product prepared in examples 1-3;
FIG. 5 shows that the Ni-Fe alloy sheet with Ni-Fe hydrotalcite nano-array composite structure grown in example 1 is placed in an electrochemical three-electrode testing system to be used as an electrolytic water oxygen evolution electrode;
FIG. 6 is a graph of the electrochemical performance of the nickel-iron hydrotalcite nano-array composite structure prepared in example 1;
fig. 7 is a graph of the stability performance of the nickel iron hydrotalcite nano array composite structure in example 1.
Detailed Description
The following further describes embodiments of the present invention with reference to the drawings.
Example 1
a) Pretreating a nickel-iron alloy sheet: repeatedly washing the nickel-iron alloy sheet with water and ethanol for 5-6 times to remove surface impurities, placing the nickel-iron alloy sheet in absolute ethanol for ultrasonic treatment for 3 minutes, taking out the nickel-iron alloy sheet, and repeatedly washing the nickel-iron alloy sheet with ultrapure water for 4 times; then ultrasonic acidification and activation are carried out in 1mol/L hydrochloric acid for 5 minutes, and the mixture is taken out and repeatedly washed for 5 times by ultrapure water; then placing the mixture in an oven at 80 ℃ for drying for 60 minutes;
b) preparation of reaction solution: taking a mixed solution of 5 ml of water and 25 ml of methanol as a solvent, adding 0.6 g of hexadecyl trimethyl ammonium bromide and 0.0168 g of potassium hydroxide into the solvent, and stirring at normal temperature until the hexadecyl trimethyl ammonium bromide and the potassium hydroxide are completely dissolved to obtain a reaction solution;
c) placing the nickel-iron alloy sheet dried in the step a) into a 40 ml polytetrafluoroethylene lining, pouring the reaction solution obtained in the step b) into the lining, placing the lining into a 150 ℃ oven after the reaction kettle is assembled, and carrying out hydrothermal reaction for 6 hours;
d) taking the reaction kettle out of the oven, obtaining a nickel-iron alloy sheet from the polytetrafluoroethylene lining, repeatedly washing the nickel-iron alloy sheet for 4 times by using water and ethanol, drying at room temperature, and growing on the surface of the nickel-iron alloy sheet to obtain a nickel-iron hydrotalcite nano array composite structure which can be used as an electrolytic water oxygen evolution reaction catalyst;
and (3) placing the nickel-iron alloy sheet with the grown nickel-iron hydrotalcite nano array composite structure in an electrochemical three-electrode test system to be used as an electrolytic water oxygen evolution electrode.
Examples 2 to 5
Examples 2 to 5 were prepared in the same manner as in example 1 except that the volumes of water and methanol in the preparation of the reaction solution in step b) were changed, and the reaction temperature and reaction time parameters in step c) were varied, and the specific reaction conditions were as shown in Table 1.
Fig. 1 shows that the ferronickel alloy sheet substrate has a significant three-dimensional pore structure; fig. 2 shows that the composite structure of the nife-based nano array prepared in this example 1 is a good acicular nano array structure, with uniform size and uniform dispersion; the smoother surface acicular array structure is clearly visible in fig. 3.
The nickel-iron hydrotalcite nano array composite structure prepared in the embodiments 1-5 of the invention is used as an electrochemical performance test of an electrolytic water oxygen evolution reaction catalyst according to the following method:
1) adopting a three-electrode system, taking 0.3cm2The nickel-iron hydrotalcite-based electrolytic water oxygen evolution catalyst is directly used as a working electrode, a counter electrode is a platinum sheet electrode, a saturated calomel electrode is used as a reference electrode, and an electrochemical test is carried out on a Chenghua (CHI 760E) electrochemical workstation. The electrolyte is 1mol/L potassium hydroxide solution, oxygen is introduced into the electrolyte for 30 minutes before the test for saturation treatment, and the oxygen atmosphere is maintained in the test process.
2) Linear sweep voltammetry test: the scanning speed was 5mV/s, and the conversion was made into the electrode potential with respect to the reversible hydrogen electrode, which was calculated by the formula:
overpotential + electrode potential +0.059 pH +0.2415-1.23 (V);
3) and (3) stability testing: applying 10mA/cm on the same electrode2Current density of (2), potential-time curves were recorded for 16 hours, followed by sequential application of 20mA/cm2、50mA/cm2The potential-time curve was recorded for 16 hours.
The electrochemical performance test of the nickel-iron hydrotalcite nano-array composite structure used as the catalyst for the electrolytic water oxygen evolution reaction in the embodiment 1 is shown in fig. 6, and the overpotential of the oxygen evolution reaction is obviously reduced. Respectively applying 10mA/cm2、20mA/cm2And 50mA/cm2The measured stability after the current density is shown in figure 7, and the prepared nickel iron hydrotalcite nano array composite structure has excellent stability in different voltage ranges.
The nickel-iron hydrotalcite nano array composite structure prepared in the embodiment 1-5 is used as a catalyst for water electrolysis oxygen evolution reaction, and reaches 10mA/cm in 1mol/L KOH solution at a sweep rate of 5mV/s2The required applied bias is shown in table 1 below:
TABLE 1
| Numbering | Water/ml | Methanol/ml | Reaction temperature/. degree.C | Reaction time/h | Applied bias voltage/mV |
| Example 1 | 5 | 25 | 150 | 6 | 210 |
| Example 2 | 10 | 20 | 150 | 8 | 220 |
| Example 3 | 15 | 15 | 120 | 6 | 240 |
| Example 4 | 20 | 10 | 180 | 6 | 230 |
| Example 5 | 25 | 5 | 150 | 6 | 255 |
Claims (9)
1. A method for synthesizing a nickel iron hydrotalcite nano array composite structure by an in-situ self-sacrifice template is characterized by comprising the following specific operations:
a) pretreating a nickel-iron alloy sheet: repeatedly washing the nickel-iron alloy sheet with water and ethanol to remove surface impurities, placing the nickel-iron alloy sheet in absolute ethanol for ultrasonic treatment for 1-5 minutes, taking out the nickel-iron alloy sheet, and repeatedly washing the nickel-iron alloy sheet with ultrapure water; then ultrasonic acidification activation is carried out in 1mol/L hydrochloric acid for 1-6 minutes, and the product is taken out and repeatedly washed by ultrapure water; then placing the mixture in an oven at 60-80 ℃ to dry for 60-80 minutes;
b) preparation of reaction solution: taking a mixed solution of 5-25 ml of water and 25-5 ml of methanol as a solvent, adding 0.6 g of hexadecyl trimethyl ammonium bromide and 0.01-0.02 g of potassium hydroxide into the solvent, and stirring at normal temperature until the hexadecyl trimethyl ammonium bromide and the potassium hydroxide are completely dissolved to obtain a reaction solution;
c) placing the nickel-iron alloy sheet dried in the step a) into a 40 ml polytetrafluoroethylene lining, pouring the reaction solution obtained in the step b) into the lining, placing the lining into a 120-plus 180 ℃ drying oven after the reaction kettle is assembled, and carrying out hydrothermal reaction for 4-8 hours;
d) taking the reaction kettle out of the oven, obtaining a nickel-iron alloy sheet from the polytetrafluoroethylene lining, repeatedly washing the nickel-iron alloy sheet with water and ethanol, drying at room temperature, and growing on the surface of the nickel-iron alloy sheet to obtain a nickel-iron hydrotalcite nano array composite structure;
the nickel iron hydrotalcite nano array composite structure has a three-dimensional needle-like nano array structure.
2. The method for synthesizing the nickel-iron hydrotalcite nano-array composite structure from the sacrificial template in situ according to claim 1, wherein in the pretreatment of the nickel-iron alloy sheet in the step a), the nickel-iron alloy sheet is subjected to ultrasonic treatment with absolute ethyl alcohol for 3 minutes, ultrasonic acidification and activation with 1mol/L hydrochloric acid for 3-5 minutes, repeatedly washed with ultrapure water and then dried in an oven at 80 ℃ for 60 minutes.
3. The method for synthesizing the nickel-iron hydrotalcite nano-array composite structure from the sacrificial template in situ according to claim 1, wherein in the step b), a mixed solution of 5 ml of water and 25 ml of methanol is used as a solvent, and 0.0168 g of potassium hydroxide is added to create an alkaline atmosphere.
4. The method for synthesizing the nickel-iron hydrotalcite nano-array composite structure from the sacrificial template in situ according to claim 1, wherein in the step c), the reaction kettle is placed in an oven and undergoes hydrothermal reaction at a high temperature of 160-180 ℃ for 6-8 hours.
5. The method for synthesizing the ferronickel hydrotalcite nano-array composite structure by the self-sacrifice template in situ according to claim 1, wherein the mass content of iron in the ferronickel alloy sheet is 70%, and the size of the ferronickel alloy sheet is 3 x 2cm2。
6. The method for synthesizing the nickel-iron hydrotalcite nano-array composite structure from the sacrificial template in situ according to claim 1, wherein the number of the repeated washing times is 4-6 times.
7. A nickel iron hydrotalcite nano-array composite structure prepared by the method of any one of the claims 1 to 6, having a three-dimensional acicular nano-array structure.
8. The use of the nickel iron hydrotalcite nano array composite structure of claim 7 as a catalyst for an electrolytic water oxygen evolution reaction.
9. An electrolytic water oxygen evolution electrode, the nickel-iron alloy sheet with the growing nickel-iron hydrotalcite nano-array composite structure prepared by the method of any one of claims 1 to 6 is placed in an electrochemical three-electrode testing system and is used as the electrolytic water oxygen evolution electrode in an alkaline medium.
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| CN112853392B (en) * | 2021-01-11 | 2022-03-18 | 清华大学深圳国际研究生院 | Alkaline electrolyzed water anode and preparation method thereof |
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| CN113186557A (en) * | 2021-04-30 | 2021-07-30 | 重庆工业职业技术学院 | In-situ preparation method of water electrolysis oxygen evolution catalytic electrode, electrode and application |
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