CN111697241A - Nickel selenide composite material loaded with nickel iron tannate and preparation method and application thereof - Google Patents
Nickel selenide composite material loaded with nickel iron tannate and preparation method and application thereof Download PDFInfo
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- CN111697241A CN111697241A CN201910194943.5A CN201910194943A CN111697241A CN 111697241 A CN111697241 A CN 111697241A CN 201910194943 A CN201910194943 A CN 201910194943A CN 111697241 A CN111697241 A CN 111697241A
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- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229920002253 Tannate Polymers 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 119
- 229910052759 nickel Inorganic materials 0.000 claims description 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000000758 substrate Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 17
- 239000001263 FEMA 3042 Substances 0.000 claims description 17
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 17
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 17
- 229940033123 tannic acid Drugs 0.000 claims description 17
- 235000015523 tannic acid Nutrition 0.000 claims description 17
- 229920002258 tannic acid Polymers 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000002070 nanowire Substances 0.000 claims description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 11
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 11
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 10
- 239000006260 foam Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 150000003346 selenoethers Chemical class 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000010411 electrocatalyst Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- 239000011669 selenium Substances 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 229910001510 metal chloride Inorganic materials 0.000 description 6
- 239000012467 final product Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- -1 transition metal selenide Chemical class 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 229910003460 diamond Inorganic materials 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- 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
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a nickel selenide composite material loaded with nickel iron tannate as well as a preparation method and application thereof. The composite material of the invention has the advantages of low cost, low synthesis temperature, high product purity, large specific surface area, large generated current and good oxygen generation performance when being used as an electrocatalyst.
Description
Technical Field
The invention relates to the technical field of transition metal selenide nanometer materials, in particular to a nickel selenide electro-catalysis composite material loaded with nickel iron tannate, and a preparation method and application thereof.
Background
In recent years, with the explosion of energy crisis, the development of new energy has become a major challenge in the present society. Electrocatalytic water decomposition is considered as one of the most attractive methods for producing renewable fuels, and has very important research value and application prospect for relieving the problems of energy shortage and environmental pollution faced by the current society. In the electrolytic water reaction, the cathode and the anode respectively carry out two different oxidation-reduction reactions of hydrogen production and oxygen production, and the oxygen evolution reaction on the anode generally shows poor activity due to slow kinetics caused by multi-electron transfer. An effective solution to this problem is to deposit a suitable oxygen evolution promoter on the surface of the anode, thereby effectively reducing the reaction overpotential. And the performance and stability of the electrocatalyst can be effectively improved by constructing the heterostructure.
At present, the traditional catalyst for electrocatalytic oxygen evolution reaction is mainly a material containing noble metals such as platinum, ruthenium, palladium and the like, and the application cost is greatly increased. Because of the properties of good stability, abundant reserves, easy preparation, environmental friendliness and the like of the transition metal selenide, the transition metal oxygen compound is widely applied to the aspects of hydrogen production by water electrolysis, oxygen production, oxygen reduction, carbon dioxide reduction and the like. Therefore, the development of oxygen evolution promoters that are efficient, stable, low overpotential, high conversion, and capable of generating large currents remains a great challenge.
Disclosure of Invention
The invention aims to provide a composite material which takes a nickel-iron tannate complex as a cocatalyst and improves the oxygen production performance of nickel selenide electrocatalytic decomposition water, and a preparation method and application thereof, aiming at the technical defects in the prior art. According to the invention, the complex formed by tannic acid and transition metal (iron and nickel) ions is used as an oxygen evolution promoter, so that the performance of electrocatalytic decomposition of water to generate oxygen of the nickel selenide nano forest is obviously improved.
The technical purpose of the invention is realized by the following technical scheme.
A nickel selenide composite material loaded with nickel iron tannate comprises a foamed nickel substrate, wherein a nickel selenide nanowire structure (forest structure) is deposited on the surface of the foamed nickel substrate, and a nickel iron tannate complex layer is arranged outside the nickel selenide nanowire structure.
Preferably, the nickel iron tannate-loaded nickel selenide composite material has a diameter of 10 to 20nm, preferably 15 to 18 nm; the thickness of the nickel selenide inner layer formed by the nickel selenide nanowire structure is 6-12 nm, and preferably 8-10 nm; the nickel iron tannate complex layer is composed of nickel iron tannate complex, and has a thickness of 4-8 nm, preferably 5-6 nm.
A preparation method of nickel selenide composite material loaded with nickel iron tannate comprises the following steps:
step 1, depositing a nickel selenide nanowire structure on the surface of a foam nickel substrate;
in the step 1, placing a foamed nickel substrate in a mixed solution of selenium powder, ethylenediamine and water, wherein the mass-volume ratio of the selenium powder to the ethylenediamine to the water is (0.04-0.06) g: (1.5-2.5) ml: (2.0-4.0) ml, placing in a hydrothermal reaction kettle, reacting at 150-180 ℃ for 3-5H, centrifuging and drying to obtain a black precipitate product loaded on a foam nickel substrate, namely a nickel selenide nanowire structure, specifically referring to the prior art of' Ni3Se2 nanoesters/Ni foam as a hydrophyllic, metallic, and selected-supported bifurcate electrochemical interaction for body H2andO2generations，Nano Energy 24(2016)103–110”。
In step 1, the foamed nickel substrate is soaked in acetone solution, water and 3M HCl aqueous solution in sequence and sonicated for 10-20 minutes.
Step 2, placing the foamed nickel substrate obtained in the step 1 in a mixed aqueous solution of nickel chloride and ferric chloride for standing so as to enable the nickel chloride and the ferric chloride to be adsorbed on the nickel selenide nanowire structure of the foamed nickel substrate;
in step 2, the molar ratio of nickel chloride to ferric chloride is (1-5): 1, preferably (3-5): 1.
and 3, sequentially adding an aqueous solution of tannic acid and an aqueous solution of sodium hydroxide into the reaction system obtained in the step 2 to react to obtain the nickel selenide composite material loaded with tannic acid nickel iron.
In step 3, tannic acid is used as a ligand to participate in coordination with metal ions, and the tannic acid is excessive to enable the metal ions, namely nickel and iron, to participate in the reaction.
In step 3, sodium hydroxide is used to adjust the pH to give a better coordination environment for the tannin ligands, and the pH is adjusted to 8 to 10, preferably 9 to 10, after the addition of sodium hydroxide.
In the step 3, 9mg/mL of tannic acid aqueous solution and 2mol/L of sodium hydroxide aqueous solution are selected, a container filled with foamed nickel is gently shaken and kept standing for 30 minutes without interference, and the nickel selenide electrocatalytic composite material loaded with nickel iron tannate as a final product is obtained by washing with water and naturally airing
The nickel selenide composite material loaded with nickel iron tannate is applied to electrocatalytic decomposition of water to produce oxygen. The nickel selenide composite material loaded with nickel iron tannate is used as an anode, and the current is attenuated by 10-15% in 24 hours. The invention discloses application of nickel iron tannate as a load to improve the performance of nickel selenide in electrocatalytic decomposition of water oxygen.
Compared with the prior art, the invention has the following beneficial effects:
(1) reacting selenium powder, ethylenediamine and water in the step 1, and generating a layer of black precipitate on a foam nickel substrate through a hydrothermal reaction to obtain a nickel selenide nano forest; in the step 2, placing the nickel selenide nano forest in a metal chloride solution until adsorption balance is achieved; and 3, carrying out a deposition reaction on the foamed nickel substrate with the surface of the nickel selenide nanometer forest, which is adsorbed with the metal chloride, with a tannic acid solution and a sodium hydroxide solution to obtain the nickel selenide nanometer forest structure loaded with nickel iron tannate.
(2) Nickel selenide electrocatalyst (marked as NiFe-TA @ Ni) loaded with nickel iron tannate3Se2) Has the advantages of low cost, low synthesis temperature, high product purity, large specific surface area, large generated current, good oxygen production performance and the like.
(3)NiFe-TA@Ni3Se2The nickel-iron tannate complex has more active sites and a stable structure, can accelerate the transfer and transmission of ions when being used as an oxygen production promoter, and has obvious advantages in the aspect of anode electrocatalytic oxygen production.
Drawings
FIG. 1 is a NiFe-TA @ Ni prepared by the present invention3Se2Scanning Electron Microscope (SEM) photographs of the nano forest composite.
FIG. 2 is a NiFe-TA @ Ni prepared by the present invention3Se2Transmission Electron Microscope (TEM) pictures of nano forest composite materials.
FIG. 3 is a NiFe-TA @ Ni prepared by the present invention3Se2X-ray diffraction (XRD) pattern of nano forest composite.
FIG. 4 is a NiFe-TA @ Ni prepared by the present invention3Se2Nano forestLinear Sweep Voltammetry (LSV) profile of the composite.
FIG. 5 is a NiFe-TA @ Ni prepared by the present invention3Se2Stability test pattern of nano forest composite material under condition of 1.55V.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. The chemical reagents used in the invention are analytically pure selenium powder, ethylenediamine, ferric chloride, nickel chloride, sodium hydroxide, tannic acid and concentrated hydrochloric acid; the hydrothermal reaction kettle in step 2 is generally a stainless steel reaction kettle with polytetrafluoroethylene as a lining.
Example 1:
step 1, cutting a foamed nickel substrate into 1 × 3cm2After which the foamed nickel substrate was soaked in acetone solution, water and 3M aqueous HCl solution in sequence and sonicated for 15 minutes.
And 2, mixing 0.05g of selenium powder, 2.0ml of ethylenediamine and 3.0ml of water in a stainless steel hydrothermal kettle, and stirring for 15 minutes. And (3) putting the clean foamed nickel substrate treated in the step (1) into a hydrothermal kettle, sealing the hydrothermal kettle, and reacting for 5 hours at the temperature of 180 ℃.
And 3, cooling the hydrothermal kettle in the step 2, respectively washing the foam nickel substrate with black precipitates on the surface by using water and alcohol, and naturally drying.
And 4, placing the foamed nickel with the black nickel selenide product on the surface obtained in the step 3 into an empty 20mL container, adding 2.5mL of 10mM ferric chloride and 7.5mL of 10mM nickel chloride, reacting for 10 minutes, and allowing the foamed nickel to be adsorbed onto the foamed nickel with the black nickel selenide product on the surface.
And 5, rapidly adding 10mL of 9mg/mL tannic acid solution and 0.1mL of 2mol/L sodium hydroxide solution to the foamed nickel which is prepared in the step 4 and has the metal chloride adsorbed surface and is a black nickel selenide product in sequence, gently shaking the 20mL container filled with the foamed nickel in the step 5, standing and depositing for 30 minutes under the condition of no interference, washing with water and naturally airing to obtain the final product nickel selenide electro-catalytic composite material loaded with nickel iron tannate.
Example 2:
step 1, cutting a foamed nickel substrate into 1 × 3cm2After which the foamed nickel substrate was soaked in acetone solution, water and 3M aqueous HCl solution in sequence and sonicated for 15 minutes.
And 2, mixing 0.05g of selenium powder, 2.0ml of ethylenediamine and 3.0ml of water in a stainless steel hydrothermal kettle, and stirring for 15 minutes. And (3) putting the clean foamed nickel substrate treated in the step (1) into a hydrothermal kettle, sealing the hydrothermal kettle, and reacting for 5 hours at the temperature of 170 ℃.
And 3, cooling the hydrothermal kettle in the step 2, respectively washing the foam nickel substrate with black precipitates on the surface by using water and alcohol, and naturally drying.
And 4, placing the foamed nickel with the black nickel selenide product on the surface obtained in the step 3 into an empty 20mL container, adding 2.5mL of 10mM ferric chloride and 7.5mL of 10mM nickel chloride, reacting for 10 minutes, and allowing the foamed nickel to be adsorbed onto the foamed nickel with the black nickel selenide product on the surface.
And 5, rapidly adding 10mL of 9mg/mL tannic acid solution and 0.1mL of 2mol/L sodium hydroxide solution to the foamed nickel which is prepared in the step 4 and has the metal chloride adsorbed surface and is a black nickel selenide product in sequence, gently shaking the 20mL container filled with the foamed nickel in the step 5, standing and depositing for 30 minutes under the condition of no interference, washing with water and naturally airing to obtain the final product nickel selenide electro-catalytic composite material loaded with nickel iron tannate.
Example 3:
step 1, cutting a foamed nickel substrate into 1 × 3cm2After which the foamed nickel substrate was soaked in acetone solution, water and 3M aqueous HCl solution in sequence and sonicated for 15 minutes.
And 2, mixing 0.05g of selenium powder, 2.0ml of ethylenediamine and 3.0ml of water in a stainless steel hydrothermal kettle, and stirring for 15 minutes. And (3) putting the clean foamed nickel substrate treated in the step (1) into a hydrothermal kettle, sealing the hydrothermal kettle, and reacting for 5 hours at the temperature of 160 ℃.
And 3, cooling the hydrothermal kettle in the step 2, respectively washing the foam nickel substrate with black precipitates on the surface by using water and alcohol, and naturally drying.
And 4, placing the foamed nickel with the black nickel selenide product on the surface obtained in the step 3 into an empty 20mL container, adding 2.5mL of 10mM ferric chloride and 7.5mL of 10mM nickel chloride, reacting for 10 minutes, and allowing the foamed nickel to be adsorbed onto the foamed nickel with the black nickel selenide product on the surface.
And 5, rapidly adding 10mL of 9mg/mL tannic acid solution and 0.1mL of 2mol/L sodium hydroxide solution to the foamed nickel which is prepared in the step 4 and has the metal chloride adsorbed surface and is a black nickel selenide product in sequence, gently shaking the 20mL container filled with the foamed nickel in the step 5, standing and depositing for 30 minutes under the condition of no interference, washing with water and naturally airing to obtain the final product nickel selenide electro-catalytic composite material loaded with nickel iron tannate.
Example 4:
step 1, cutting a foamed nickel substrate into 1 × 3cm2After which the foamed nickel substrate was soaked in acetone solution, water and 3M aqueous HCl solution in sequence and sonicated for 15 minutes.
And 2, mixing 0.05g of selenium powder, 2.0ml of ethylenediamine and 3.0ml of water in a stainless steel hydrothermal kettle, and stirring for 15 minutes. And (3) putting the clean foamed nickel substrate treated in the step (1) into a hydrothermal kettle, sealing the hydrothermal kettle, and reacting for 5 hours at the temperature of 150 ℃.
And 3, cooling the hydrothermal kettle in the step 2, respectively washing the foam nickel substrate with black precipitates on the surface by using water and alcohol, and naturally drying.
And 4, placing the foamed nickel with the black nickel selenide product on the surface obtained in the step 3 into an empty 20mL container, adding 2.5mL of 10mM ferric chloride and 7.5mL of 10mM nickel chloride, reacting for 10 minutes, and allowing the foamed nickel to be adsorbed onto the foamed nickel with the black nickel selenide product on the surface.
And 5, rapidly adding 10mL of 9mg/mL tannic acid solution and 0.1mL of 2mol/L sodium hydroxide solution to the foamed nickel which is prepared in the step 4 and has the metal chloride adsorbed surface and is a black nickel selenide product in sequence, gently shaking the 20mL container filled with the foamed nickel in the step 5, standing and depositing for 30 minutes under the condition of no interference, washing with water and naturally airing to obtain the final product nickel selenide electro-catalytic composite material loaded with nickel iron tannate.
And (4) analyzing results:
NiFe-TA @ Ni prepared by using SEM and TEM pairs3Se2And (3) carrying out morphology characterization on the nano forest composite material, wherein the morphology of the composite material is nano forest (figure 1), the diameter of the composite material is 10-20 nanometers, and the thicknesses of the nickel selenide inner layer and the nickel iron tannate outer layer are respectively 6-12 nanometers and 4-8 nanometers (figure 2).
The prepared NiFe-TA @ Ni3Se2 nano forest composite material is tested by XRD (attached figure 3), the obtained diffraction peaks can correspond to diamond nickel selenide with the card number of JCPDS:85-0754 and simple substance nickel with the card number of JCPDS:04-0850 one by one, and no other impurity peaks exist, which shows that the obtained product is really pure nickel selenide grown on the foamed nickel; because the tannic acid ligand is amorphous, the XRD pattern hardly changes before and after encapsulation.
NiFe-TA @ Ni prepared by adopting method3Se2The specific steps of the electrocatalysis test of the nano forest composite material are as follows: the electrocatalytic water decomposition test is carried out in a standard three-electrode system, the counter electrode is a glassy carbon electrode, the reference electrode is a mercury/mercury oxide (1M potassium hydroxide) electrode, and the electrolyte is a 1M potassium hydroxide solution. When NiFe-TA @ Ni3Se2When the nano forest composite material is used as a working electrode to carry out oxygen evolution reaction (figure 4), the magnitude of current of the material is improved by orders of magnitude before and after the material is loaded with NiFe-TA under the same potential, which shows that the nickel selenide can effectively increase the current after the material is loaded with NiFe-TA. At the same time, the current-time curve of the electrocatalytic oxygen production process was also measured (FIG. 5) to evaluate the stability of the anode, NiFe-TA @ Ni3Se2The photocurrent is only attenuated by 15 percent, which shows that the nickel selenide can effectively increase the stability of oxygen generation of the anode after being loaded with NiFe-TA.
The process parameters were carried out according to the inventionAll can realize NiFe-TA @ Ni3Se2Nano forest composite material was prepared and showed substantially the same properties as the examples. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. The nickel selenide composite material loaded with nickel iron tannate is characterized by comprising a foamed nickel substrate, wherein a nickel selenide nanowire structure is deposited on the surface of the foamed nickel substrate, and a nickel iron tannate complex layer is arranged outside the nickel selenide nanowire structure.
2. The nickel iron tannate-loaded selenide composite material according to claim 1, wherein the nickel iron tannate-loaded selenide composite material has a diameter of 10-20 nm, preferably 15-18 nm.
3. The nickel selenide composite material loaded with nickel iron tannate according to claim 1, wherein the thickness of the nickel selenide inner layer formed by the nickel selenide nanowire structure is 6-12 nm, preferably 8-10 nm.
4. Nickel-iron tannate-loaded nickel selenide composite material according to claim 1, wherein the nickel-iron tannate complex layer consists of a nickel-iron tannate complex and has a thickness of 4 to 8nm, preferably 5 to 6 nm.
5. A preparation method of nickel selenide composite material loaded with nickel iron tannate is characterized by comprising the following steps:
step 1, depositing a nickel selenide nanowire structure on the surface of a foam nickel substrate;
step 2, placing the foamed nickel substrate obtained in the step 1 in a mixed aqueous solution of nickel chloride and ferric chloride for standing so as to enable the nickel chloride and the ferric chloride to be adsorbed on the nickel selenide nanowire structure of the foamed nickel substrate;
and 3, sequentially adding an aqueous solution of tannic acid and an aqueous solution of sodium hydroxide into the reaction system obtained in the step 2 to react to obtain the nickel selenide composite material loaded with tannic acid nickel iron.
6. The method for preparing nickel iron tannate-loaded nickel selenide composite material according to claim 5, wherein in the step 1, the foamed nickel substrate is placed in a mixed solution of selenium powder, ethylenediamine and water, wherein the mass-volume ratio of the selenium powder, the ethylenediamine and the water is (0.04-0.06) g: (1.5-2.5) ml: (2.0-4.0) ml, placing the mixture in a hydrothermal reaction kettle, reacting for 3-5h at the temperature of 150-180 ℃, and centrifugally drying to obtain a black precipitate product loaded on a foam nickel substrate, namely the nickel selenide nanowire structure.
7. The preparation method of nickel iron tannate-loaded nickel selenide composite material according to claim 5, wherein in the step 2, the molar ratio of nickel chloride to ferric chloride is (1-5): 1, preferably (3-5): 1.
8. the method for preparing nickel selenide composite material loaded with nickel iron tannate according to claim 5, wherein in the step 3, tannic acid is used as a ligand and participates in coordination with metal ions, and is excessive in order to make all metal ions of nickel and iron participate in reaction; the sodium hydroxide is used to adjust the pH to give a better coordination environment for the tannic acid ligand, and the pH is adjusted to 8 to 10, preferably 9 to 10, after the sodium hydroxide is added.
9. The use of a nickel-iron tannate-loaded nickel-selenide composite material for the electrocatalytic decomposition of water to produce oxygen according to any one of claims 1 to 4, wherein the nickel-iron tannate-loaded nickel-selenide composite material is used as an anode with a current decay of 10 to 15% for 24 hours.
10. The nickel iron tannate is applied to improving the performance of nickel selenide in producing oxygen by electrocatalytic decomposition of water as a load.
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| CN116273161A (en) * | 2023-02-20 | 2023-06-23 | 四川大学 | Preparation method and application of tannin foam loaded nano zero-valent iron catalyst |
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| US20160379764A1 (en) * | 2015-06-25 | 2016-12-29 | William Marsh Rice University | Ni(OH)2 NANOPOROUS FILMS AS ELECTRODES |
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| CN116273161A (en) * | 2023-02-20 | 2023-06-23 | 四川大学 | Preparation method and application of tannin foam loaded nano zero-valent iron catalyst |
| CN116273161B (en) * | 2023-02-20 | 2024-04-05 | 四川大学 | Preparation method and application of tannin foam loaded nano zero-valent iron catalyst |
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Application publication date: 20200922 |