CN111939945A - CoSe2NiSe2Preparation of-CC composite material and application of electrolytic water hydrogen evolution performance thereof - Google Patents
CoSe2NiSe2Preparation of-CC composite material and application of electrolytic water hydrogen evolution performance thereof Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 48
- 239000001257 hydrogen Substances 0.000 title claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 35
- 239000004744 fabric Substances 0.000 claims abstract description 35
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 claims abstract description 11
- PZFKDUMHDHEBLD-UHFFFAOYSA-N oxo(oxonickeliooxy)nickel Chemical compound O=[Ni]O[Ni]=O PZFKDUMHDHEBLD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 58
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 23
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- 238000002791 soaking Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 13
- 229910017052 cobalt Inorganic materials 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 11
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 4
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- 229910021581 Cobalt(III) chloride Inorganic materials 0.000 claims description 3
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- 238000012545 processing Methods 0.000 claims description 3
- 150000001869 cobalt compounds Chemical class 0.000 claims description 2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- B01J35/33—
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a CoSe2/NiSe2-CC composite material and a process for its preparation. The method comprises the following steps of treating the carbon cloth as a substrate: the carbon cloth is treated by ultrasonic cleaning; step two, Ni2O3/Co2O3-preparation of CC; step three, CoSe2/NiSe2-preparation of CC. The invention synthesizes high-density and uniformly distributed CoSe2/NiSe2CC composite, CoSe of different doping ratios2/NiSe2-CC composite material, the electrocatalytic activity of the sample is best when Co: Ni (molar ratio) =7: 3. At the same over-potentialBelow, CoSe2/NiSe2the-CC-73 has better electrocatalytic activity, can more effectively generate electrolyzed water for hydrogen evolution, and has the highest hydrogen production efficiency under the same electrode system.
Description
Technical Field
The invention relates to renewable and clean energy, in particular to CoSe2NiSe2Preparation of CC composite material and application of electrolytic water hydrogen evolution performance thereof.
Background
The energy problem is a great problem facing human beings, particularly the exhaustion of fossil fuels, and the substitute of fossil energy is urgently needed. Clean hydrogen can replace fossil fuel, and is one of potential ways to solve energy problems. The electrolytic water hydrogen evolution is the hot field of research on hydrogen production at present, the most efficient electrocatalyst is precious metal platinum at present, but platinum belongs to rare metal, and the content of the platinum is low, and the price is high, so that the efficient electrocatalyst with low price and wide range is urgently needed to be found. Recent studies have shown that transition metals have unpaired d electrons and unfilled d orbitals with good catalytic properties. Researches find that the metal lattice can have great influence on the activity of electrocatalytic hydrogen evolution, which has great significance on the selection of the electrocatalysts for hydrogen evolution. The invention selects the selenide composite material as the catalytic active substance, utilizes the carbon cloth with good conductivity as the substrate, leads the composite material to grow on the carbon cloth evenly, and researches the appearance and the electrocatalysis performance of the composite material.
Disclosure of Invention
In view of the above, the present invention provides a CoSe alloy to overcome the disadvantages of the prior art2NiSe2A preparation method of the-CC composite material, which has good performance of hydrogen evolution by water electrolysis.
In order to achieve the purpose, the invention adopts the following technical scheme:
CoSe2/NiSe2-CC composite, CoSe2/NiSe2Crystal grains are uniformly grown on the carbon cloth.
In a preferred embodiment of the present invention, the molar ratio of Co to Ni is 3: 7.
The CoSe2/NiSe2The preparation method of the-CC composite material comprises the step of reacting a substrate with a cobalt-nickel mixed solution to prepare a precursor Ni2O3/Co2O3-CC, precursor Ni2O3/Co2O3reacting-CC with selenium powder to prepare NiSe2/Co Se2-CC; preferably, the sum of the molar concentrations of cobalt and nickel in the cobalt-nickel mixed solution is 0.5 mol/L.
As a preferred embodiment of the present invention, the CoSe is2/NiSe2-a method for the preparation of a CC composite comprising the steps of,
step one, processing carbon cloth as a substrate: the carbon cloth is treated by ultrasonic cleaning;
step two, Ni2O3/Co2O3Preparation of CC: washing the carbon cloth obtained in the step one with ethanol, adding a cobalt-nickel mixed solution for reaction, taking out the carbon cloth, washing the carbon cloth with ethanol, and soaking the carbon cloth with a KOH solution to complete one cycle; the process is cycled for 6 times respectively to prepare samples; drying and calcining the sample to obtain a precursor Ni2O3/Co2O3-CC；
Preferably, the cobalt-nickel mixed solution takes a water-soluble trivalent cobalt compound as a cobalt source and a water-soluble trivalent nickel compound as a nickel source; preferably, with CoCl3·6H2O as a source of cobalt, NiN2O6·6H2O is taken as a nickel source, and the total mole number of Co and Ni is 0.01-0.1mol/L of aqueous solution; 0.05mol/L aqueous solution;
preferably, the reaction time is 3-10 min; more preferably, the reaction time is 5 min;
preferably, the KOH concentration used is 0.5 mol/L;
preferably, the soaking time is 3-10 min; more preferably, the soaking time is 5 min;
preferably, the drying is drying treatment for 20-30 hours in a vacuum drying oven with the constant temperature of 50-70 ℃; more preferably, the drying is drying treatment for 24 hours in a vacuum drying oven with a constant temperature of 60 ℃;
preferably, the calcination is carried out on the sample on a porcelain boat and/or in an inert gas atmosphere and/or the calcination is carried out at a temperature of 250-350 ℃ andor a tubular furnace is used and/or the calcination time is 150-200 min; more preferably, the inert gas is N2、Ar; more preferably, the calcination is carried out at a temperature of 300 ℃ and/or using a tube furnace and/or for a calcination time of 180 min;
step three, CoSe2/NiSe2Preparation of CC: dissolving selenium powder in ethylene glycol, and mixing with precursor Ni2O3/Co2O3Cooling to room temperature after CC high-temperature reaction, soaking the synthesized sample in a solvent, and drying to obtain a sample;
preferably, the high-temperature reaction is carried out at 200-300 ℃ and/or is carried out for 35-45 h; more preferably, the high-temperature reaction is carried out at 250 ℃ and/or after 40 hours of reaction;
preferably, the drying is carried out in a vacuum drying oven at 60 ℃ for 24 hours.
In the first step, the ultrasonic cleaning is performed by sequentially using methanol, ethanol and deionized water, and/or each solvent for 10-20min, more preferably 15 min.
In the second step, the molar ratio of Co to Ni in the cobalt-nickel mixed solution is 1:9-9: 1; preferably, the molar ratio of Co to Ni is 7: 3.
In the third step, the sample is soaked in the solvent in the CS23-10nin, more preferably 5 min; soaking in ethanol for 3-10min, preferably 5 min; soaking in deionized water for 3-10min, preferably 5 min; soaking in ethanol for 3-10min, preferably 5 min.
In a preferred embodiment of the present invention, in step three, the selenium powder is 2 to 3.5 times equivalent of the mole number of cobalt/nickel, and preferably, the selenium powder is 2 times equivalent of the mole number of cobalt/nickel.
The invention also provides CoSe2/NiSe2-CC composite material is applied to electrolysis of water for hydrogen evolution.
As a preferred embodiment of the present invention, the NiSe is used2Preparing a three-electrode system by using a-CC composite material as a working electrode, Hg/HgO as a reference electrode and a platinum sheet as an auxiliary electrode, and dissolving in an alkaline aqueous solutionThe liquid is electrolyte and is used for electrolytic water hydrogen evolution reaction; preferably, KOH solution is used as electrolyte; more preferably, the KOH solution is an aqueous solution with the concentration of 1 mol/L.
The invention has the beneficial effects that:
in the invention, CoSe with high density and uniform distribution is synthesized2/NiSe2-a CC composite; when the molar ratio of Co to Ni is 3:7, the sample is a crystal particle which uniformly grows on carbon cloth, when the content of cobalt is gradually increased and the content of nickel is gradually reduced to be Co to Ni (molar ratio) 7:3, the appearance of the sample is gradually clustered into a cluster needle shape, the surface area is larger, the electron transmission rate can be improved, and the electrochemical hydrogen evolution performance is better. The results of measurement and analysis by an electrochemical workstation show that CoSe with different doping ratios2/NiSe2-CC composite, with the best electrocatalytic activity of the sample when Co: Ni (molar ratio) is 7: 3. At the same over-potential, CoSe2/NiSe2the-CC-73 has better electrocatalytic activity, can more effectively generate electrolyzed water for hydrogen evolution, and has the highest hydrogen production efficiency under the same electrode system.
Drawings
FIG. 1 is a powder X-ray diffraction pattern of a sample: respectively as (a): CoSe2/NiSe2-CC-19；(b)：CoSe2/NiSe2-CC-37；(c)：CoSe2/NiSe2-CC-55；(d)：CoSe2/NiSe2-CC-73；(e)：CoSe2/NiSe2-CC-91；
FIG. 2 is (a) CoSe2/NiSe2-scanning electron microscopy of low power SEM samples of CC-19 composite.
FIG. 3 (b) CoSe2/NiSe2-scanning electron microscopy of high power SEM samples of CC-19 composite.
FIG. 4 (c) CoSe2/NiSe2-scanning electron microscopy of low power SEM samples of CC-37 composite.
FIG. 5 (d) CoSe2/NiSe2-scanning electron microscopy of high power SEM samples of CC-37 composite.
FIG. 6 is (e): CoSe2/NiSe2-scanning electron microscopy of low power SEM samples of CC-55 composite.
FIG. 7 is (f): CoSe2/NiSe2-scanning electron microscopy of high power SEM samples of CC-55 composite.
FIG. 8 is (g): CoSe2/NiSe2-scanning electron microscopy of a low power SEM sample of CC-73 composite.
FIG. 9 (h) CoSe2/NiSe2-scanning electron microscopy of high power SEM samples of CC-73 composite.
FIG. 10 is (i): CoSe2/NiSe2-scanning electron microscopy of a low power SEM sample of CC-91 composite.
FIG. 11 is (j): CoSe2/NiSe2-scanning electron microscopy of a high power SEM sample of CC-91 composite.
FIG. 12 (k) CoSe2/NiSe2Element distribution diagram one of the CC-73 composite.
FIG. 13 shows (l) CoSe2/NiSe2Element distribution diagram two of the CC-73 composite.
FIG. 14 (m) CoSe2/NiSe2Element distribution diagram three of CC-73 composite.
FIG. 15 shows that (n): CoSe2/NiSe2Element distribution diagram four of the CC-73 composite.
FIG. 16 is (o): CoSe2/NiSe2Element distribution diagram five of the CC-73 composite.
FIG. 17 is CeSe2/NiSe2-linear voltammogram of CC composite: respectively as (a): CoSe2/NiSe2-CC-19；(b)： CoSe2/NiSe2-CC-37；(c)：CoSe2/NiSe2-CC-55；(d)：CoSe2/NiSe2-CC-73；(e)： CoSe2/NiSe2-CC-91；
Fig. 18 tafel polarization curve (a): CoSe2/NiSe2-CC-19；(b)：CoSe2/NiSe2-CC-37；(c)： CoSe2/NiSe2-CC-55；(d)：CoSe2/NiSe2-CC-73；(e)：CoSe2/NiSe2-CC-91；
FIG. 19 is sample CoSe2Cyclic voltammogram of/NiSe 2-CC-73: sample (a): CoSe2/NiSe2-CC-19；(b)： CoSe2/NiSe2-CC-37；(c)：CoSe2/NiSe2-CC-55；(d)：CoSe2/NiSe2-CC-73；(e)： CoSe2/NiSe2-CC-91；
Fig. 20 is an electric double layer capacitance diagram of a sample: respectively as (a): CoSe2/NiSe 2-CC-19; (b) the method comprises the following steps CoSe2/NiSe 2-CC-37; (c): CoSe2/NiSe 2-CC-55; (d) the method comprises the following steps CoSe2/NiSe 2-CC-73; (e) the method comprises the following steps CoSe2/NiSe 2-CC-91;
fig. 21 ac impedance graph (a): CoSe2/NiSe2-CC-19；(b)：CoSe2/NiSe2-CC-37；(c)： CoSe2/NiSe2-CC-55；(d)：CoSe2/NiSe2-CC-73；(e)：CoSe2/NiSe2-CC-91；
Detailed Description
The invention is further described below with reference to the figures and examples.
1 laboratory reagents and instruments
TABLE 1 chemicals used in the experiments
TABLE 2 Main instruments used in the experiment
2. Procedure of experiment
2.1 carbon cloth treatment
Cutting 5 parts of 2.0cm × 3.0cm carbon cloth at room temperature, using as the substrate of the synthetic material, and respectively performing ultrasonic treatment with methanol, ethanol and deionized water for 15 min. And placing the treated carbon cloth in deionized water or drying and storing for later use.
2.2 preparation of the precursor
Weighing KOH solid, dissolving with deionized water, and preparing a certain amount of 0.05mol/L KOH solution. Taking CoCl3·6H2O as a source of experimental cobalt, NiN2O6·6H2Taking O as a nickel source for an experiment, weighing samples according to the molar ratio of Co to Ni of 1:9, 3:7, 5:5, 7:3 and 9:1, enabling the total molar number of Co and Ni to be 0.05mol, and putting the samples into five clean beakers. 80mL of deionized water was added to prepare a 0.05mol/L solution, which was designated as A, B, C, D, E.
Further processing the prepared five parts of solution, wherein each part of solution is averagely divided into three parts, and each part of solution reacts with the processed carbon cloth; firstly, putting the treated carbon cloth into a metal salt solution for reaction for 5min, and then washing the carbon cloth by using an ethanol solution; soaking the carbon cloth washed by the ethanol in a KOH solution for 5min, taking out and washing the carbon cloth by the ethanol, and circulating for 6 times according to the reaction process to obtain five groups of samples with different proportions, wherein each group comprises 3 parallel samples. The sample is a carbon cloth with a metal salt sample attached to the surface.
And (3) drying the carbon cloth with the surface attached with the metal salt sample in a vacuum drying oven at the constant temperature of 60 ℃ for 24 hours. Taking out and placing in a porcelain boat at N2Calcining at 300 ℃ in an atmospheric tubular furnace, and taking out after 180min to obtain the precursor.
2.3 CoSe2/NiSe2Preparation of-CC
Weighing 5 parts of 1mmol Se powder, placing the powder in a black polytetrafluoroethylene reaction kettle, respectively adding 15mL of ethylene glycol, and stirring for 15 min. And respectively putting the calcined intermediates into a kettle for numbering. Taking out after hydrothermal reaction for 40h at 250 ℃ in a muffle furnace, cleaning, and respectively placing in CS2Soaking in ethanol solution for 5min, soaking in distilled water for 5min, and soaking in ethanol solution for 5 min. Taking out and drying in a vacuum drying oven at 60 ℃ for 24h, taking out to obtain CoSe2/NiSe2The CC product, a sample with Co: Ni (molar ratio) 1:9 during precursor synthesis, was named CoSe2/NiSe2Samples of-CC-19 and Co: Ni (molar ratio) ═ 3:7 were designated CoSe2/NiSe2Samples of-CC-37 and Co: Ni (molar ratio) ═ 5:5 were designated CoSe2/NiSe2-CC-55, Co: Ni (mol)Sample with molar ratio of 9:1 was named CoSe2/NiSe2-CC-73、CoSe2/NiSe2-CC-91。
2.4 characterization of the samples
Determining the intermediate oxide and the final sample morphology structure using a cold field emission scanning electron microscope; determining the crystal structure and the phase composition of the sample by using an X-ray powder diffractometer (XRD); the valence state of the element is determined by X-ray photoelectron spectroscopy (XPS) to realize the qualitative analysis of the element on the surface of the sample.
2.5 preparation of electrolyte
Preparing 1mol/L KOH alkaline electrolyte, and introducing nitrogen for 30min before testing in an electrochemical workstation. To attach CoSe2/NiSe2The method is characterized in that a three-electrode system is manufactured by taking carbon cloth of a sample as a working electrode, Hg/HgO as a reference electrode and a platinum sheet as an auxiliary electrode, 1mol/L alkaline KOH solution is taken as electrolyte, and the electrochemical performance of the three-electrode system is represented by an electrochemical workstation and an electrochemical test system, for example: sexual sweep voltammetry, Tafel polarization curve analysis and linear cyclic voltammetry.
3 results and discussion
XRD analysis
The crystal structure of the sample can be obtained by analyzing the X-ray powder diffraction pattern. From the graph, it can be found that the indices of the crystal plane are (101), (111), (220), (330), (121), (311), (230), and (321) at 2 θ of 30.20 °, 33.93 °, 36.04 °, 37.44 °, 42.99 °, 51.01 °, 55.73 °, and 58.27 °, respectively. Wherein the indexes of the crystal form are diffraction peaks and NiSe of (101), (111), (312) and (121)2The PDF standard card (JCPDS, No.18-0886) is completely matched; diffraction peaks and CoSe labeled (311), (230), (321)2PDF standard card (JCPDS, No.09-0234)[7][8]And (5) the consistency is achieved. Through comparative analysis of the components, the characteristic diffraction peak intensity is strongest and the crystallinity is better when the doping amounts of Co and Ni are equal. According to the XRD experimental result, we successfully synthesize the CeSe2/NiSe2-a CC composite.
3.2 SEM and EDS analysis
Scanning electron microscopy using cold field emissionAnd (4) directly observing the surface micro-topography structure of the synthesized composite material by using a mirror (FE-SEM). FIGS. 2-16 are scanning electron microscope and energy spectrum analysis graphs of CoSe/NiSe-CC composites with different molar ratios of Co and Ni. Wherein FIGS. 2-3 (a-b) are sample CeSe2/NiSe2CC-19 low and high power images, wherein the appearance is flaky and the attachment density is high; FIGS. 4-5 (c-d) are sample CeSe2/NiSe2CC-37 low-power and high-power images, the appearance is granular, and the images are distributed on the carbon cloth more uniformly; FIGS. 6-7 (e-f) are the sample CeSe2/NiSe2CC-55 low-power and high-power graphs, wherein the sample is agglomerated and unevenly distributed; FIGS. 8-9 (g-h) are sample CeSe2/NiSe2CC-73 hypo-and high-power images, the sample presents a needle-shaped cluster structure and is distributed more uniformly; FIGS. 10-11 (i-j) are sample CeSe2/NiSe2CC-91 low and high power graph, from which it can be seen that the sample is cubic and closely attached. From the SEM image obtained from the sample, it can be seen that when the Co: Ni (molar ratio) is 3:7, the sample is uniformly grown on carbon cloth, which indicates that when the cobalt content is gradually increased and the nickel content is gradually decreased, the Co: Ni (molar ratio) is 7:3, the sample morphology is gradually clustered into cluster needle shape, the surface area is larger, the electron transfer rate can be increased, and the electrochemical hydrogen evolution performance is better. To further determine the composition of the composite material, the elemental distribution of the sample was qualitatively and quantitatively analyzed using an energy spectrometer (EDS). The energy spectra of e-f show that Co, Ni and Se are uniformly distributed on the surface of the carbon cloth, which indicates that the synthesized CoSe/NiSe-CC composite material is consistent with the pre-synthesized product.
3.3 Linear sweep voltammetry
The test was carried out by using CHI660E electrochemical workstation, using 1.0cm × 1.0cm carbon cloth to which the sample was attached as a working electrode, a platinum sheet as an auxiliary electrode, Hg/HgO as a reference electrode, to form a three-electrode system, using 1mol/L KOH solution as an electrolyte, and carrying out an electrocatalytic hydrogen evolution test at a sweep rate of 50 mV. As can be seen from the graph, at a current density of 10mA/cm2When the overpotentials (vs RHE) of the samples (a to e) were-0.353 mV, -0.311mV, -0.538mV, -0.198mV, -0.299mV, respectively. So when the molar ratio isThe lowest decomposition voltage required for Co to Ni to 7 to 3 had a lower initial overvoltage, indicating that a lower voltage could be applied for the electrocatalytic hydrogen evolution reaction, thereby reacting the electrochemical reaction. The results analyzed that CoSe was present at the same overpotential2/NiSe2the-CC-73 has better electrocatalytic activity, can more effectively generate electrolyzed water for hydrogen evolution, and has the highest hydrogen production efficiency under the same electrode system.
3.4 Tafel profiling
Fig. 18 is a tafel polarization curve (a) for the composite: CoSe2/NiSe2-CC-19；(b)：CoSe2/NiSe2-CC-37； (c)：CoSe2/NiSe2-CC-55；(d)：CoSe2/NiSe2-CC-73；(e)：CoSe2/NiSe2-CC-91. Because the Tafel slope represents the relation curve of different electrode potentials and current densities, the slope is obtained by analyzing the cathode polarization curve in the experiment, and the smaller the slope is, the easier the reaction is to occur and the faster the electrocatalytic hydrogen evolution rate is under the same current density can be obtained by comparing the slopes of different samples. A Tafel curve is tested by using a CHI660E electrochemical workstation, a 1.0cm multiplied by 1.0cm carbon cloth attached with a sample is used as a working electrode, a platinum sheet is used as an auxiliary electrode, Hg/HgO is used as a reference electrode to form a three-electrode system, a 1mol/L KOH solution is used as an electrolyte, and an electro-catalytic hydrogen evolution test is carried out at a sweep rate of 50 mV. From the comparison of the slopes in the figure, it can be found that when the Co: Ni (molar ratio) is 5:5, the tafel slope is the largest, the electrocatalytic hydrogen evolution rate is slow, and hydrogen production is not facilitated. Meanwhile, when the molar ratio of Co to Ni is 7:3, the Tafel slope is minimum, the electrocatalytic hydrogen evolution rate is high, and hydrogen production is facilitated, which shows that CoSe2/NiSe2CC-73 has a faster electro-catalytic hydrogen production rate, can more effectively generate electro-catalytic hydrogen production, and has the highest hydrogen production efficiency under the same electrode system.
3.5 Linear Cyclic voltammetry
The electrocatalytic hydrogen evolution means that hydrogen is generated at the cathode of an electrode by electrolyzing water by using an efficient catalyst through an electrochemical method, and the electrochemical performance of an electrode material can be analyzed by using cyclic voltammetry. FIG. 5 is a cyclic voltammogram of CoSe/NiSe (7: 3) -CC samples at different scan rates, from which it can be seen that the cyclic voltammograms of the samples are close to the ideal rectangles. The graph shows that the electrode potentials at-0.55V to-0.35V are scanned repeatedly in a triangular waveform over time at different rates.
Fig. 20 is sample (a): CoSe2/NiSe2-CC-19；(b)：CoSe2/NiSe2-CC-37；(c)：CoSe2/NiSe2-CC-55； (d)：CoSe2/NiSe2-CC-73；(e)：CoSe2/NiSe2Dual capacitance plot of CC-91. Because ECSA ═ CdCharacteristic capacitance of/C (C)s) Constant, double layer capacitance (C)dl) The larger the capacitance, the larger the effective electrochemical area (ECSA), so from comparative analysis of the electric double layer capacitance of each sample in the right hand graph: when the doping ratio of Co to Ni is 5:5 hours, the electric double layer capacitance is minimum, and the sample CoSe2/NiSe2The effective electrochemical area of CC-55 is minimum, the catalytic active sites are few, and the catalytic activity is poor; when the doping ratio of Co to Ni is 7:3 hours, the electric double layer capacitance is maximum, sample CoSe2/NiSe2The effective electrochemical area of the CC-55 is the largest, the catalytic activity sites are many, and the catalytic activity is the best.
Fig. 21 is a graph of the ac impedance of samples, sample (a): CoSe2/NiSe2-CC-19；(b)： CoSe2/NiSe2-CC-37；(c)：CoSe2/NiSe2-CC-55；(d)：CoSe2/NiSe2-CC-73；(e)： CoSe2/NiSe2-ac impedance profile of CC-91 composite. One of the important methods for researching electrochemistry by an electrochemical alternating current impedance method is to take small-amplitude sine wave current as a disturbance signal to enable an electrode system to generate response similar to a linear relation, measure an impedance spectrum of the electrode system in a wide frequency range and research the electrode system by the method. The initial resistance in the figure is the solution resistance, approximately a semi-circle curve, the diameter of which can represent the electron transfer resistance (R) of the electrode systemCT) From this, the electron transfer rate of the electrode system can be seen. From comparison in the figure, it can be found that when Co: Ni (molar ratio) is 5:5, the sample (c): CoSe2/NiSe2The CC-55 electron transfer resistance is the largest, the electron transfer rate of an electrode system is the slowest, the electrocatalytic hydrogen evolution rate is the slowest, and hydrogen production is not facilitated. Meanwhile, we see that when the molar ratio of Co to Ni is 7:3, the electron transfer resistance of the sample is small, the electrocatalytic hydrogen evolution rate is high, and the hydrogen production is facilitated, which indicates that the sample (d) CoSe2/NiSe2the-CC-73 has a faster electron transfer rate, can generate electro-catalysis hydrogen more effectively, and has the highest hydrogen production efficiency under the same electrode system.
4 conclusion
In the experiment, a hydrothermal synthesis method is adopted to successfully synthesize CoSe with high density and uniform distribution2/NiSe2-a CC composite. The results of measurement and analysis by an electrochemical workstation show that CoSe with different doping ratios2/NiSe2-CC composite, with the best electrocatalytic activity of the sample when Co: Ni (molar ratio) is 7: 3. The reason is that:
(1) by analyzing the linear scanning pattern, the electrode system is CoSe under the same overpotential2/NiSe2The CC-73 has better electrocatalytic activity, and the system can generate corresponding electrochemical reaction under lower voltage, so that the electrolyzed water can be more effectively generated for hydrogen evolution.
(2) And analyzing the cyclic voltammetry curve and the electric double layer capacitance to obtain the following formula (1) when the doping ratio of Co to Ni is 7:3 hours, the electric double layer capacitance is maximum, sample CoSe2/NiSe2The effective electrochemical area of the surface of the CC-73 is the largest, the catalytic activity sites are many, and the catalytic activity is the best.
(3) By analyzing the Tafel polarization curve, when Co: Ni (molar ratio) is 7:3, the sample CoSe2/NiSe2The overpotential for hydrogen evolution of-CC-73 is small, the hydrogen evolution rate of the electrocatalytic reaction is higher, and the hydrogen production is more facilitated, which shows that CoSe2/NiSe2the-CC-73 has a faster electrolyzed water hydrogen evolution rate, can more effectively generate electrolyzed water hydrogen evolution, and has the highest hydrogen evolution efficiency under the same electrode system.
(4) By analyzing the AC impedance spectrum, the sample (d) CoSe was measured at the same solution resistance2/NiSe2-CC-73 is smallerThe electron transfer resistance is beneficial to the transmission of electrons, so that the electron transfer rate is high, and the electrolyzed water can be better generated to generate hydrogen evolution.
Finally, the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting, and other modifications or equivalent substitutions made by the technical solutions of the present invention by those of ordinary skill in the art should be covered within the scope of the claims of the present invention as long as they do not depart from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. CoSe2/NiSe2-CC composite, CoSe2/NiSe2Crystal grains are uniformly grown on the carbon cloth.
2. The CoSe of claim 12/NiSe2-CC composite material, characterized in that Co to Ni molar ratio =3: 7.
3. The CoSe of claim 1 or 22/NiSe2The preparation method of the-CC composite material comprises the step of reacting a substrate with a cobalt-nickel mixed solution to prepare a precursor Ni2O3/Co2O3-CC, precursor Ni2O3/Co2O3reacting-CC with selenium powder to prepare NiSe2/Co Se2-CC; preferably, the sum of the molar concentrations of cobalt and nickel in the cobalt-nickel mixed solution is 0.5 mol/L.
4. The CoSe of claim 32/NiSe2-a method for the preparation of a CC composite, characterized in that it comprises the following steps,
step one, processing carbon cloth as a substrate: the carbon cloth is treated by ultrasonic cleaning;
step two, Ni2O3/Co2O3Preparation of CC: washing the carbon cloth obtained in the step one with ethanol, adding a cobalt-nickel mixed solution for reaction, taking out the carbon cloth, washing the carbon cloth with ethanol, and soaking the carbon cloth with a KOH solution to complete one cycle; respectively circulating for 6 times according to the process to preparePreparing a sample; drying and calcining the sample to obtain a precursor Ni2O3/Co2O3-CC；
Preferably, the cobalt-nickel mixed solution takes a water-soluble trivalent cobalt compound as a cobalt source and a water-soluble trivalent nickel compound as a nickel source; preferably, with CoCl3·6H2O as a source of cobalt, NiN2O6·6H2O is taken as a nickel source, and the total mole number of Co and Ni is 0.01-0.1mol/L of aqueous solution; 0.05mol/L aqueous solution;
preferably, the reaction time is 3-10 min; more preferably, the reaction time is 5 min;
preferably, the KOH concentration used is 0.5 mol/L;
preferably, the soaking time is 3-10 min; more preferably, the soaking time is 5 min;
preferably, the drying is drying treatment for 20-30 hours in a vacuum drying oven with the constant temperature of 50-70 ℃; more preferably, the drying is drying treatment for 24 hours in a vacuum drying oven with a constant temperature of 60 ℃;
preferably, the calcination is to calcine the sample on a porcelain boat and/or in an inert gas atmosphere and/or the calcination is to use a tube furnace and/or the calcination time is 150-200min and/or the temperature is 250-350 ℃; more preferably, the inert gas is N2、Ar; more preferably, the calcination is carried out at a temperature of 300 ℃ and/or using a tube furnace and/or for a calcination time of 180 min;
step three, CoSe2/NiSe2Preparation of CC: dissolving selenium powder in ethylene glycol, and mixing with precursor Ni2O3/Co2O3Cooling to room temperature after CC high-temperature reaction, soaking the synthesized sample in a solvent, and drying to obtain a sample;
preferably, the high-temperature reaction is carried out at 200-300 ℃ and/or is carried out for 35-45 h; more preferably, the high-temperature reaction is carried out at 250 ℃ and/or after 40 hours of reaction;
preferably, the drying is carried out in a vacuum drying oven at 60 ℃ for 24 hours.
5. The preparation method according to claim 4, wherein in the first step, the ultrasonic cleaning is sequentially performed by using methanol, ethanol, deionized water and/or each solvent for 10-20min, and more preferably 15 min.
6. The preparation method according to claim 4, wherein in the second step, the molar ratio of Co to Ni in the cobalt-nickel mixed solution is 1:9-9: 1; preferably, the molar ratio of Co to Ni is 7: 3.
7. The method according to claim 4, wherein the soaking in the solvent is performed in the third step by sequentially placing the synthesized sample in the CS23-10nin, more preferably 5 min; soaking in ethanol for 3-10min, preferably 5 min; soaking in deionized water for 3-10min, preferably 5 min; soaking in ethanol for 3-10min, preferably 5 min.
8. The preparation method according to claim 4, wherein in step three, the selenium powder is 2-3.5 times equivalent of cobalt/nickel mol number, preferably, the selenium powder is 2 times equivalent of cobalt/nickel mol number.
9. Subjecting the CoSe of claim 1 or 22/NiSe2-CC composite or CoSe obtained by the process of any of claims 3 to 82/NiSe2Application of the CC composite to the electrolysis of water for hydrogen evolution.
10. Use according to claim 9, wherein the NiSe is used as a carrier of a fuel cell2the-CC composite material is used as a working electrode, Hg/HgO is used as a reference electrode, a platinum sheet is used as an auxiliary electrode to manufacture a three-electrode system, and an alkaline aqueous solution is used as electrolyte to perform an electrolytic water hydrogen evolution reaction; preferably, KOH solution is used as electrolyte; more preferably, the KOH solution is an aqueous solution with the concentration of 1 mol/L.
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