CN111841577A - Preparation method and application of flaky copper-cobalt bimetallic sulfide catalytic material - Google Patents
Preparation method and application of flaky copper-cobalt bimetallic sulfide catalytic material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 22
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 19
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010949 copper Substances 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- IOEJYZSZYUROLN-UHFFFAOYSA-M Sodium diethyldithiocarbamate Chemical compound [Na+].CCN(CC)C([S-])=S IOEJYZSZYUROLN-UHFFFAOYSA-M 0.000 claims abstract 10
- 239000000243 solution Substances 0.000 claims description 37
- 238000005406 washing Methods 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 241000446313 Lamella Species 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 13
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 2
- APMQGWUYHMFEMM-UHFFFAOYSA-L cobalt(2+);n,n-diethylcarbamodithioate Chemical compound [Co+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S APMQGWUYHMFEMM-UHFFFAOYSA-L 0.000 abstract 1
- OBBCYCYCTJQCCK-UHFFFAOYSA-L copper;n,n-diethylcarbamodithioate Chemical compound [Cu+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S OBBCYCYCTJQCCK-UHFFFAOYSA-L 0.000 abstract 1
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 abstract 1
- 229950004394 ditiocarb Drugs 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 229910016507 CuCo Inorganic materials 0.000 description 11
- 239000010411 electrocatalyst Substances 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 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
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000037230 mobility Effects 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal sulfides Chemical class 0.000 description 1
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- 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
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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Abstract
The invention belongs to the technical field of new energy materials and electrochemical catalysis, and relates to a preparation method of a flaky copper-cobalt bimetallic sulfide catalytic material and application of the flaky copper-cobalt bimetallic sulfide catalytic material in electrolytic water oxygen evolution catalytic reaction. The catalytic material is of the same concentrationMixing the aqueous solution of sodium diethyldithiocarbamate (NaDDTC) with the aqueous solution of copper nitrate and cobalt nitrate, stirring, centrifuging, drying, and getting the precursor of copper and cobalt, i.e. copper diethyldithiocarbamate (Cu (DDTC)2) And cobalt diethyldithiocarbamate (Co (DDTC)2). Then using octylamine as solvent, Cu (DDTC)2And Co (DDTC)2Stirring the raw materials, and then reacting the mixture in a high-pressure reaction kettle to obtain CuCo2S4An oxygen evolution catalyst. The catalyst is prepared by a simple solvothermal method, has controllable and higher electro-catalysis performance and electrochemical stability, and can be applied to the fields of oxygen evolution reaction, zinc-air battery electrode catalytic materials and the like.
Description
Technical Field
The invention belongs to the technical field of new energy materials and electrochemical catalysis, and relates to a preparation method of a flaky copper-cobalt bimetallic sulfide catalytic material and application of the flaky copper-cobalt bimetallic sulfide catalytic material in electrolytic water oxygen evolution catalytic reaction.
Background
With the continuous development of society, the demand for exploring sustainable and efficient renewable energy sources to replace traditional fossil fuels is increasingly urgent. Electrochemical, photocatalytic water splitting reactions in various energy conversion and storage technologies, such as hydrogen production, renewable fuel cells, and the like, have attracted extensive research attention. However, in the electrochemical hydrogen production reaction by water splitting, because the anodic Oxygen Evolution Reaction (OER) has a four-electron transfer process and a kinetic process thereof is slow, how to reduce the OER overpotential is one of the key links for producing hydrogen by electrolyzing water. By using a proper and efficient electrocatalyst, the overpotential of the OER can be effectively reduced, so that the performance and efficiency of hydrogen production by electrochemical water decomposition are greatly improved, and the search for a high-performance and high-stability oxygen evolution reaction electrocatalyst is urgent. A common electrocatalyst for OER currently in commercial use is RuO2And IrO2Although they have relatively high oxygen evolution catalytic activity, they have problems of single catalytic activity, poor stability, low storage capacity, high cost and the like, and limit the large-scale application thereof. Therefore, non-noble transition metal sulfides are widely studied as electrocatalysts for OER.
However, not noble transition monometallic sulfides, e.g. CoS, Ni3S2Etc. still has less active sites, poor conductivity and more efficient electrical contact with electrolyteLow and unstable under the catalytic reaction condition. But copper-based multimetal sulfides have abundant reserves, low cost, and higher carrier concentrations, as well as significant charge carrier mobilities, as well as variable morphology, composition, and stoichiometry. Therefore, the functional copper-cobalt bimetallic sulfide is designed and developed, and the morphology is controlled, so that the synergistic effect between copper and cobalt atoms is enhanced to optimize the electronic structure of a metal site, and an OER electrocatalyst with high active sites, high conductivity, strong stability and the like is expected to be obtained.
Disclosure of Invention
Aiming at the defects in the prior art, in order to prepare the flaky copper-cobalt bimetallic sulfide oxygen evolution catalytic material, a precursor of copper and cobalt is prepared in a solution blending mode, and then the flaky copper-cobalt bimetallic sulfide oxygen evolution catalytic material is prepared by a solvothermal method. The invention can provide inspiration for developing the research of polymetallic sulfide and polymetallic composite sulfide catalytic materials, is expected to solve the problems of high price, single catalytic performance, poor stability, incapability of meeting the industrial production and the like of the OER catalyst, and can obtain the OER electrocatalyst with high active sites, high conductivity, strong stability and the like.
In order to achieve the above purpose, the invention provides a preparation method of a flaky copper-cobalt bimetallic sulfide catalytic material, which specifically comprises the following steps:
(1) mixing the NaDDTC solution and the copper nitrate solution, stirring, centrifugally washing, and drying in vacuum to obtain a precursor Cu (DDTC)2；
(2) Mixing the NaDDTC solution and the cobalt nitrate solution, stirring, centrifugally washing, and drying in vacuum to obtain a precursor Co (DDTC)2；
(3) Firstly, taking Cu (DDTC) obtained in the step (1) and the step (2)2And Co (DDTC)2Ultrasonically dispersing the solid powder in octylamine solution, stirring to obtain a mixed solution, transferring the mixed solution into a high-pressure reaction kettle, cooling to room temperature after the reaction is finished, centrifugally washing, and freeze-drying to obtain CuCo2S4And (3) obtaining the product.
In the step (1), the concentration of the NaDDTC solution is 0.38-0.42mol/L, the concentration of the copper nitrate solution is 0.25mol/L, and the volume ratio of the NaDDTC solution to the copper nitrate solution is 100: 80-85.
In the step (2), the concentration of the NaDDTC solution is 0.38-0.42mol/L, the concentration of the cobalt nitrate solution is 0.25mol/L, and the volume ratio of the NaDDTC solution to the cobalt nitrate solution is 100: 80-85.
In the step (1) and the step (2), the vacuum drying temperature is 60 ℃ and the vacuum drying time is 24 hours; the centrifugal washing refers to that the centrifugal washing is carried out for a plurality of times by sequentially using deionized water and absolute ethyl alcohol.
In the step (3), in the mixed solution, Cu (DDTC)2The concentration of (A) is 0.003 mol/L; co (DDTC)2The concentration of (B) is 0.006 mol/L.
In the step (3), the reaction temperature in the high-pressure reaction kettle is 150 ℃ and 190 ℃, and the reaction time is 5-10 h.
In the step (3), the freeze drying temperature is less than or equal to-45 ℃, and the freezing time is 24 hours.
In the step (3), the centrifugal washing refers to centrifugal washing for several times by sequentially using acetone, absolute ethyl alcohol and deionized water.
The copper-cobalt bimetallic sulfide prepared by the method is of a nano flaky structure, and the width of the sheet is 100-200 nm.
The flaky copper-cobalt bimetallic sulfide catalytic material prepared by the invention is applied to electrocatalysis in the anodic oxygen evolution reaction of electrolyzed water.
The invention has the beneficial effects that:
(1) the synthesis method and the required equipment are simple, the operation is convenient and the cost is low.
(2) The nano flaky copper-cobalt bimetallic sulfide catalytic material prepared by the method develops researches on polymetallic sulfides and polymetallic composite sulfide catalytic materials, and has very excellent OER catalytic activity; at a current density of 10mA cm-2The overpotential of the OER is 290mV, and the Tafel slope is only 81.3mV dec-1And has better stability than the prior commercial IrO 2The catalyst can be used as a renewable fuel cell, a rechargeable zinc-air cell and an electrocatalyst in the field of water electrolysis.
Drawings
FIG. 1 shows the results of example 1Prepared CuCo2S4X-ray diffraction pattern of (a).
FIG. 2 is a scanning electron micrograph and a transmission electron micrograph of a material prepared in example 1, wherein a is CuCo prepared in example 12S4Scanning Electron micrograph of nanoplatelets, b is CuCo prepared as in example 12S4Transmission electron micrograph (c).
FIG. 3 is a CuCo prepared in example 12S4LSV curve of catalyst for oxygen evolution reaction by electrolysis of water.
FIG. 4 is a CuCo prepared in example 12S4Tafel curve diagram of nanosheet as electrolytic water oxygen evolution catalyst in 1M KOH solution, wherein the abscissa is the logarithm of the current density and the ordinate is the voltage.
FIG. 5 is a CuCo prepared in example 12S4As a catalyst for the evolution of oxygen by electrolysis of water in a 1M KOH electrolyte at a constant potential of 290mV over-potential for an electrolysis time of 40 h.
Detailed Description
It will be understood by those skilled in the art that the following examples are illustrative of the present invention only and should not be construed as limiting in any way.
The raw materials used in the invention are all conventional commercial products.
Unless otherwise specified, the Oxygen Evolution (OER) activity of the catalyst prepared according to the present invention was evaluated by the following method:
Taking 4mg of catalyst, ultrasonically dispersing in 1mL of absolute ethyl alcohol, adding 20 mu L of 5% Nafion solution, ultrasonically forming uniform slurry, then coating the slurry on a glassy carbon electrode, and carrying out an OER test after the electrode is dried.
The OER test is as follows:
1) the electrochemical system is a standard three-electrode system (a glassy carbon electrode attached with a catalyst is used as a working electrode, a carbon rod is used as an auxiliary electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode), and an electrolyte is a 1.0mol/L KOH solution.
2) Evaluating the activity of Oxygen Evolution (OER), and performing a linear sweep voltammetry test (LSV), wherein the voltage sweep range is 0-0.8V, and the sweep rate is 5mV s-1。
Example 1:
(1)Cu(DDTC)2and Co (DDTC)2Preparation of precursor powder:
taking 0.02mol of Cu (NO)3)2·6H2O was dissolved in 80ml of deionized water, and 100ml of aqueous NaDDTC solution (containing 0.04mol of NaDDTC) was slowly added thereto with magnetic stirring. Magnetically stirring at room temperature for reaction for 3h, centrifuging, washing, and vacuum drying to obtain Cu (DDTC)2Preparation of Co (DDTC) by the same method2And (3) precursor.
(2) Taking 0.1mmol Cu (DDTC)2And 0.2mmol Co (DDTC)2The powder is dispersed in 30ml of octylamine solution by ultrasonic, and is reacted for 3 hours under the condition of magnetic stirring at room temperature, and then is transferred into a 50ml high-pressure reaction kettle to be reacted for 5 hours at 180 ℃. Then after the reaction is finished and the temperature is cooled to room temperature, carrying out centrifugal washing, sequentially carrying out centrifugal washing for a plurality of times by using acetone, absolute ethyl alcohol and deionized water, then placing the obtained product in a freeze dryer, and carrying out freeze drying for 24 hours to obtain a product CuCo 2S4And (3) powder.
FIG. 1 shows the CuCo prepared2S4The X-ray diffraction (XRD) spectrogram of the catalyst is compared to obtain that all diffraction peaks of the prepared catalyst are equal to CuCo2S4Corresponds to the standard card (PDF # 42-1450). Indicating successful synthesis of the catalyst.
As can be seen from the scanning electron microscope image a and the transmission electron microscope image b in FIG. 2, CuCo2S4Has the characteristic of lamellar structure, and the lamellar structure is formed by mutually stacking small lamellae, and the width of the lamellae is 100-200 nm.
CuCo can be seen from the LSV curve in FIG. 32S4At a current density of 10mA cm-2The potential at that time was 1.52V and the overpotential was 290mV, indicating that CuCo2S4Has high oxygen evolution reaction capability.
CuCo can be seen from Tafel curve in FIG. 42S4Has a slope of only 81.3mV dec-1And the material has excellent oxygen evolution kinetic characteristics by having a smaller Tafel slope.
FIG. 5 is CuCo2S4Time in 1mol/L KOH solution-current profile. After the test is carried out for 40h under the constant potential of 1.52V, the current density is slightly increased relative to the initial value, which indicates that the material has good electrochemical stability.
Example 2:
(1) same as step (1) in example 1;
(2) taking 0.1mmol Cu (DDTC)2And 0.2mmol Co (DDTC)2The powder is dispersed in 30ml of octylamine solution by ultrasonic, and is reacted for 3 hours under magnetic stirring at room temperature, and then is transferred to a 50ml high-pressure reaction kettle to be reacted for 5 hours at 150 ℃. Then after the reaction is finished and the temperature is cooled to room temperature, carrying out centrifugal washing, sequentially carrying out centrifugal washing for a plurality of times by using acetone, absolute ethyl alcohol and deionized water, then placing the obtained product in a freeze dryer, and carrying out freeze drying for 24 hours to obtain a product CuCo 2S4And (3) powder.
Example 3:
(1) same as step (1) in example 1;
(2) taking 0.1mmol Cu (DDTC)2And 0.2mmol Co (DDTC)2The powder is dispersed in 30ml of octylamine solution by ultrasonic, and is reacted for 3 hours under magnetic stirring at room temperature, and then is transferred to a 50ml high-pressure reaction kettle to be reacted for 5 hours at 160 ℃. Then after the reaction is finished and the temperature is cooled to room temperature, carrying out centrifugal washing, sequentially carrying out centrifugal washing for a plurality of times by using acetone, absolute ethyl alcohol and deionized water, then placing the obtained product in a freeze dryer, and carrying out freeze drying for 24 hours to obtain a product CuCo2S4And (3) powder.
Example 4:
(1) same as step (1) in example 1;
(2) taking 0.1mmol Cu (DDTC)2And 0.2mmol Co (DDTC)2The powder is dispersed in 30ml of octylamine solution by ultrasonic, and is reacted for 3 hours under magnetic stirring at room temperature, and then is transferred to a 50ml high-pressure reaction kettle to be reacted for 5 hours at 170 ℃. Then after the reaction is finished and the temperature is cooled to room temperature, carrying out centrifugal washing, sequentially carrying out centrifugal washing for a plurality of times by using acetone, absolute ethyl alcohol and deionized water, then placing the obtained product in a freeze dryer, and carrying out freeze drying for 24 hours to obtain a product CuCo2S4And (3) powder.
Example 5:
(1) same as step (1) in example 1;
(2) taking 0.1mmol Cu (DDTC)2And 0.2mmol Co (DDTC)2The powder is dispersed in 30ml of octylamine solution by ultrasonic, and is reacted for 3 hours under magnetic stirring at room temperature, and then is transferred to a 50ml high-pressure reaction kettle to be reacted for 7 hours at 180 ℃. Then after the reaction is finished and the temperature is cooled to room temperature, carrying out centrifugal washing, sequentially carrying out centrifugal washing for a plurality of times by using acetone, absolute ethyl alcohol and deionized water, then placing the obtained product in a freeze dryer, and carrying out freeze drying for 24 hours to obtain a product CuCo 2S4And (3) powder.
Example 6:
(1) same as step (1) in example 1;
(2) taking 0.1mmol Cu (DDTC)2And 0.2mmol Co (DDTC)2The powder is dispersed in 30ml of octylamine solution by ultrasonic, and is reacted for 3 hours under the condition of magnetic stirring at room temperature, and then is transferred into a 50ml high-pressure reaction kettle to be reacted for 9 hours at 180 ℃. Then after the reaction is finished and the temperature is cooled to room temperature, carrying out centrifugal washing, sequentially carrying out centrifugal washing for a plurality of times by using acetone, absolute ethyl alcohol and deionized water, then placing the obtained product in a freeze dryer, and carrying out freeze drying for 24 hours to obtain a product CuCo2S4And (3) powder.
The above description is only an embodiment of the present invention, and is not intended to limit the present invention, and all the equivalent structures or equivalent flow transformations made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A preparation method of a flaky copper-cobalt bimetallic sulfide catalytic material comprises the following steps:
(1) mixing the NaDDTC solution and the copper nitrate solution, stirring, centrifugally washing, and drying in vacuum to obtain a precursor Cu (DDTC)2；
(2) Mixing the NaDDTC solution and the cobalt nitrate solution, stirring, centrifugally washing, and drying in vacuum to obtain a precursor Co (DDTC)2；
(3) Firstly, taking Cu (DDTC) obtained in the step (1) and the step (2) 2And Co (DDTC)2Ultrasonically dispersing solid powder in octylamine solution, stirring to obtain mixed solution, transferring into high-pressure reactor, and cooling to room temperature after reactionAfter warming, centrifugally washing, freezing and drying to obtain CuCo2S4And (3) obtaining the product.
2. The method of claim 1, wherein: in the step (1), the concentration of the NaDDTC solution is 0.38-0.42mol/L, the concentration of the copper nitrate solution is 0.25mol/L, and the volume ratio of the NaDDTC solution to the copper nitrate solution is 100: 80-85.
3. The method of claim 1, wherein: in the step (2), the concentration of the NaDDTC solution is 0.38-0.42mol/L, the concentration of the cobalt nitrate solution is 0.25mol/L, and the volume ratio of the NaDDTC solution to the cobalt nitrate solution is 100: 80-85.
4. The method of claim 1, wherein: in the step (1) and the step (2), the vacuum drying temperature is 60 ℃ and the vacuum drying time is 24 hours; the centrifugal washing refers to that the centrifugal washing is carried out for a plurality of times by sequentially using deionized water and absolute ethyl alcohol.
5. The method of claim 1, wherein: in the step (3), in the mixed solution, Cu (DDTC)2The concentration of (A) is 0.003 mol/L; co (DDTC)2The concentration of (B) is 0.006 mol/L.
6. The method of claim 1, wherein: in the step (3), the reaction temperature in the high-pressure reaction kettle is 150 ℃ and 190 ℃, and the reaction time is 5-10 h.
7. The method of claim 1, wherein: in the step (3), the freeze drying temperature is less than or equal to-45 ℃, and the freezing time is 24 hours.
8. The method of claim 1, wherein: in the step (3), the centrifugal washing refers to centrifugal washing for several times by sequentially using acetone, absolute ethyl alcohol and deionized water.
9. A flaky copper-cobalt bimetallic sulfide catalytic material is characterized in that: is prepared by the preparation method of any one of claims 1 to 8, has a nano lamellar structure, and has a lamella width of 100-200 nm.
10. Use of the flaky copper-cobalt bimetallic sulfide catalytic material of claim 9 in electrocatalysis in an anodic oxygen evolution reaction of electrolyzed water.
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