CN110624573A - Nickel-doped cobalt selenide electro-catalysis hydrogen evolution catalyst and preparation method thereof - Google Patents
Nickel-doped cobalt selenide electro-catalysis hydrogen evolution catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 41
- 239000001257 hydrogen Substances 0.000 title claims abstract description 41
- QVYIMIJFGKEJDW-UHFFFAOYSA-N cobalt(ii) selenide Chemical compound [Se]=[Co] QVYIMIJFGKEJDW-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 26
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011669 selenium Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 18
- 239000012498 ultrapure water Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 11
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000004809 Teflon Substances 0.000 claims description 9
- 229920006362 Teflon® Polymers 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 7
- 230000010287 polarization Effects 0.000 abstract description 7
- 238000002484 cyclic voltammetry Methods 0.000 abstract description 5
- 238000004140 cleaning Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 47
- 229910052759 nickel Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- -1 platinum group metals Chemical class 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GAIMSHOTKWOMOB-UHFFFAOYSA-N [Se]=[Co]=[Se] Chemical compound [Se]=[Co]=[Se] GAIMSHOTKWOMOB-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- XUKVMZJGMBEQDE-UHFFFAOYSA-N [Co](=S)=S Chemical compound [Co](=S)=S XUKVMZJGMBEQDE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
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- 238000010000 carbonizing Methods 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004769 chrono-potentiometry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Classifications
-
- 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—
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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
A nickel-doped cobalt selenide electro-catalysis hydrogen evolution catalyst and a preparation method thereof relate to an electro-catalysis hydrogen evolution catalyst and a preparation method thereof. The preparation method aims to solve the technical problems of complex preparation steps, high cost and poor safety of the existing cobalt selenide-doped electrocatalytic hydrogen evolution catalyst. The catalyst has the chemical general formula of CoxNiySe2X is 0.6 to 0.8, and y is 0.1 to 0.35. The preparation method comprises the following steps: dissolving selenium powder in potassium hydroxide solution, and adding Co (NO)3)2·6H2O、Ni(NO3)2·6H2O, EDTA-2Na and ultrapure water are evenly stirred to obtain mixed liquid; then transferring the mixture to a reaction kettle for hydrothermal reaction, and then cleaning and drying the mixtureDrying to obtain a catalyst; the overpotential of the catalyst reaches 170-195 mV VS RHE, and after 1000 circles of continuous cyclic voltammetry test, the polarization curve almost coincides with the initial curve, so that the catalyst has high stability and can be used in an electrocatalytic hydrogen evolution reaction.
Description
Technical Field
The invention relates to an electrocatalytic hydrogen evolution catalyst and a preparation method thereof.
Background
With the development of global economy, fossil fuels are gradually exhausted, and meanwhile, environmental problems such as air pollution and the like caused by the combustion of the fossil fuels force people to find clean and renewable new energy sources such as solar energy, wind energy, biological energy, hydrogen energy and the like. Among these new energy sources, hydrogen is widely concerned by people because its source is wide, the combustion product is pollution-free water, and the energy generated by hydrogen per unit mass is larger than other energy sources and the energy utilization rate is high. However, the hydrogen is generated by electrolyzing water, the dynamic process is slow, and high overpotential is often needed, so that a hydrogen evolution reaction catalyst is needed to reduce high energy consumption needed in the electrolysis process, and the water electrolysis reaction is realized efficiently. At present, platinum group metals are the best electrochemical hydrogen evolution catalysts, but the rarity and high cost of the platinum group metals also make the electrochemical hydrogen evolution catalysts difficult to popularize and use on a large scale. Among other non-noble metal catalysts, cobalt-based compounds including cobalt disulfide, cobalt selenide, cobalt carbide, and the like have attracted considerable attention in the past few years, but have poor catalytic performance. In order to further improve the electrocatalytic properties of cobalt-based compounds, they are doped and modified.
The chinese patent with application number 201810123010.2 discloses a preparation method and application of an iron-doped cobalt diselenide composite nitrogen-doped carbon material. The method comprises the steps of taking a metal organic framework ZIF-67 as a precursor, etching by utilizing ferric ions to obtain Fe-ZIF-67 modified by iron, carbonizing and selenizing the Fe-ZIF-67 by utilizing selenium steam at high temperature to obtain iron-doped cobalt diselenide (Fe-CoSe) loaded by nitrogen-doped porous carbon2@ NC) powdered electrode material. Mixing Fe-CoSe2The @ NC powder is made into slurry and brushed on the conductive carbon fiber paper to prepare Fe-CoSe2@ NC/CFP electrode. Fe-CoSe2The electrochemical catalysis hydrogen production performance indexes of the @ NC/CFP electrode are as follows: the Tafel slope is 40.9 mV/decade; up to 10mA/cm2The overpotential for the current density was-0.143V (vs RHE). The steps involved in this patent are more complex and require chemical etching and high temperature carbonization processes. Chinese patent with application number of 201910171517.XA preparation method of a nitrogen and nickel codoped cobalt selenide ultrathin nanosheet discloses a preparation method of a cobalt selenide doped material, which comprises the steps of mixing a cobalt source, a selenium source, a nickel source, a nitrogen source, water and diethylenetriamine, and carrying out a solvothermal reaction to obtain a nitrogen and nickel codoped cobalt selenide precursor; and then washing and drying the precursor to obtain the nitrogen and nickel co-doped cobalt selenide ultrathin nanosheet. The patent is simultaneously applied to the modification of cobalt selenide by metal doping and nonmetal doping, and has higher preparation cost and poor safety.
Disclosure of Invention
The invention provides a nickel-doped cobalt selenide electro-catalysis hydrogen evolution catalyst and a preparation method thereof, aiming at solving the technical problems of complex preparation steps, high cost and poor safety of the existing cobalt selenide-doped electro-catalysis hydrogen evolution catalyst.
The nickel-doped cobalt selenide electro-catalytic hydrogen evolution catalyst has a chemical general formula of CoxNiySe2，x＝0.6～0.8，y＝0.1～0.35。
The preparation method of the nickel-doped cobalt selenide electro-catalytic hydrogen evolution catalyst comprises the following steps:
one, press CoxNiySe2Weighing selenium powder and Co (NO) according to the stoichiometric ratio3)2·6H2O and Ni (NO)3)2·6H2O，CoxNiySe2Wherein x is 0.6-0.8, and y is 0.1-0.35; then weighing potassium hydroxide solution, EDTA-2Na and ultrapure water;
secondly, dissolving the selenium powder in a potassium hydroxide solution, stirring for 25-35 min, and adding Co (NO)3)2·6H2O、Ni(NO3)2·6H2O, EDTA-2Na and ultrapure water, and continuously stirring for about 1-1.5 h to obtain a mixed solution;
thirdly, transferring the mixture into a Teflon reaction kettle, reacting for 10-16 h at the temperature of 160-200 ℃, and naturally cooling to room temperature;
and fourthly, washing the black precipitate obtained by the reaction with water and ethanol in sequence, and then placing the black precipitate in a vacuum oven at the temperature of 60-65 ℃ for 12-15 hours to obtain the nickel-doped cobalt selenide electro-catalysis hydrogen evolution catalyst.
The overpotential (the current density is 10mA cm) of the nickel-doped cobalt selenide electro-catalytic hydrogen evolution catalyst-2The time potential) reaches 170-195 mV VS RHE, the Tafel slope reaches 32-62V VS RHE, is very close to platinum, can be compared favorably with the currently accepted best platinum catalyst, and simultaneously has ultrahigh stability, after 1000 circles of continuous cyclic voltammetry test, the polarization curve is almost overlapped with the initial curve, 10000s under the overpotential condition, the current density is not obviously changed, and the stability in the acid electrolyte is good.
The nickel-doped cobalt selenide electro-catalysis hydrogen evolution catalyst has simple and complex preparation steps, low cost and safety. Can be used in electrocatalytic hydrogen evolution reaction.
Drawings
FIG. 1 shows materials CNSe-1, CNSe-2, CNSe-3, CNSe-4 and CoSe prepared in examples 1 to 4 and comparative examples 1 to 22And NiSe2A polarization graph of (a);
FIG. 2 shows materials CNSe-1, CNSe-2, CNSe-3, CNSe-4 and CoSe prepared in examples 1 to 4 and comparative examples 1 to 22And NiSe2A tafel slope plot of (a);
FIG. 3 shows materials CNSe-1, CNSe-2, CNSe-3, CNSe-4 and CoSe prepared in examples 1 to 4 and comparative examples 1 to 22And NiSe2The overpotential histogram of (a);
FIG. 4 shows materials CNSe-1, CNSe-2, CNSe-3, CNSe-4 and CoSe prepared in examples 1 to 4 and comparative examples 1 to 22And NiSe2A tafel slope histogram of (a);
FIG. 5 is a chemical formula of Co prepared in example 30.77Ni0.25Se2The polarization curve of the catalyst CNSe-3 is compared with the polarization curve after 1,000 times of continuous cyclic voltammetry;
FIG. 6 is a chemical formula of Co prepared in example 30.77Ni0.25Se2The catalyst CNSe-3 of (a) has a 10,000s current density change curve graph at a potential of-179 mV;
FIG. 7 is a chemical formula of Co prepared in example 30.77Ni0.25Se2Scanning electron micrograph of catalyst CNSe-3 (b);
FIG. 8 is a chemical formula of Co prepared in example 30.77Ni0.25Se2A transmission electron micrograph of the catalyst CNSe-3 (B).
Detailed Description
The first embodiment is as follows: the nickel-doped cobalt selenide electro-catalytic hydrogen evolution catalyst has a chemical general formula of CoxNiySe2，x＝0.6～0.8，y＝0.1～0.35。
The second embodiment is as follows: the preparation method of the nickel-doped cobalt selenide electro-catalytic hydrogen evolution catalyst comprises the following steps:
one, press CoxNiySe2Weighing selenium powder and Co (NO) according to the stoichiometric ratio3)2·6H2O and Ni (NO)3)2·6H2O，CoxNiySe2Wherein x is 0.6-0.8, and y is 0.1-0.35; then weighing potassium hydroxide solution, EDTA-2Na and ultrapure water;
secondly, dissolving the selenium powder in a potassium hydroxide solution, stirring for 25-35 min, and adding Co (NO)3)2·6H2O、Ni(NO3)2·6H2O, EDTA-2Na and ultrapure water, and continuously stirring for about 1-1.5 h to obtain a mixed solution;
thirdly, transferring the mixture into a Teflon reaction kettle, reacting for 10-16 h at the temperature of 160-200 ℃, and naturally cooling to room temperature;
and fourthly, washing the black precipitate obtained by the reaction with water and ethanol in sequence, and then placing the black precipitate in a vacuum oven at the temperature of 60-65 ℃ for 12-15 hours to obtain the nickel-doped cobalt selenide electro-catalysis hydrogen evolution catalyst.
The third concrete implementation mode: the difference between the second embodiment and the first embodiment is that the concentration of the potassium hydroxide solution in the first step is 20-25 mol/L; the rest is the same as the second embodiment.
The fourth concrete implementation mode: the second or third embodiment is different from the first embodiment in that in the first step, the molar ratio of the selenium powder to the potassium hydroxide in the potassium hydroxide solution is 1: (50-60); the other is the same as the second or third embodiment.
The fifth concrete implementation mode: the difference between this embodiment and one of the second to fourth embodiments is that in the first step, the molar ratio of the selenium powder to the EDTA-2Na is 1: (0.8 to 0.9); the other is the same as one of the second to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the second to fifth embodiments is that in the first step, the ratio of the amount of the substance of selenium powder to the volume of ultrapure water is 1 mmol: (10-12) mL; the other is the same as one of the second to fifth embodiments.
The following examples are used to demonstrate the beneficial effects of the present invention.
Example 1: the preparation method of the nickel-doped cobalt selenide electro-catalytic hydrogen evolution catalyst comprises the following steps:
weighing 2mmol selenium powder and 1.0mmol Co (NO)3)2·6H2O、0.25mmolNi(NO3)2·6H2O, weighing 5mL of potassium hydroxide solution with the concentration of 20mol/L, 1.60mmol of EDTA-2Na and 20mL of ultrapure water;
secondly, dissolving 2mmol of selenium powder in 5mL of potassium hydroxide solution with the concentration of 20mol/L, stirring for 30min, and adding 1.0mmol of Co (NO)3)2·6H2O, 0.25mmol of Ni (NO)3)2·6H2O, 1.60mmol of EDTA-2Na and 20mL of ultrapure water, and continuously stirring for about 1h to obtain a mixed solution;
thirdly, transferring the mixture into a Teflon reaction kettle, reacting for 12 hours at the temperature of 180 ℃, and naturally cooling to room temperature;
fourthly, cleaning the black precipitate obtained by the reaction with water and ethanol for 3 times respectively, and then placing the black precipitate in a vacuum oven at 60 ℃ for 12 hours to obtain the nickel-doped cobalt selenide electro-catalysis hydrogen evolution catalyst, wherein the chemical formula of the catalyst is Co0.78Ni0.13Se2And is denoted as CNSe-1.
Example 2: the preparation method of the nickel-doped cobalt selenide electro-catalytic hydrogen evolution catalyst comprises the following steps:
weighing 2.00mmol selenium powder and 1.00mmol Co (NO)3)2·6H2O, 0.50mmol of Ni (NO)3)2·6H2O; then 5mL of 20mol/L potassium hydroxide solution, 1.60mmol of EDTA-2Na and 20mL of ultrapure water are weighed;
secondly, dissolving 2.00mmol of selenium powder in 5mL of potassium hydroxide solution with the concentration of 20mol/L, stirring for 30min, and adding 1.00mmol of Co (NO)3)2·6H2O, 0.50mmol of Ni (NO)3)2·6H2O, 1.60mmol of EDTA-2Na and 20mL of ultrapure water, and continuously stirring for about 1-1.5 h to obtain a mixed solution;
thirdly, transferring the mixture into a Teflon reaction kettle, reacting for 12 hours at the temperature of 180 ℃, and naturally cooling to room temperature;
fourthly, washing the black precipitate obtained by the reaction with water and ethanol for 3 times respectively, and then placing the black precipitate in a vacuum oven at 65 ℃ for 12 hours to obtain the nickel-doped cobalt selenide electro-catalysis hydrogen evolution catalyst, wherein the chemical formula of the catalyst is Co0.73Ni0.20Se2And is denoted as CNSe-2.
Example 3: the preparation method of the nickel-doped cobalt selenide electro-catalytic hydrogen evolution catalyst comprises the following steps:
weighing 2.00mmol selenium powder and 1.00mmol Co (NO)3)2·6H2O, 0.75mmol of Ni (NO)3)2·6H2O, 5mL of 20mol/L potassium hydroxide solution, 1.60mmol of EDTA-2Na and 20mL of ultrapure water;
secondly, dissolving 2.00mmol of selenium powder in 5mL of potassium hydroxide solution with the concentration of 20mol/L, stirring for 30min, and adding 1.00mmol of Co (NO)3)2·6H2O, 0.75mmol of Ni (NO)3)2·6H2O, 1.60mmol of EDTA-2Na and 20mL of ultrapure water, and continuously stirring for about 1-1.5 h to obtain a mixed solution;
thirdly, transferring the mixture into a Teflon reaction kettle, reacting for 12 hours at the temperature of 180 ℃, and naturally cooling to room temperature;
fourthly, the black precipitate obtained by the reaction is sequentially cleaned by water and ethanolWashing for 3 times, and then placing in a vacuum oven at 60 ℃ for 12 hours to obtain the nickel-doped cobalt selenide electro-catalysis hydrogen evolution catalyst, wherein the chemical formula of the catalyst is Co0.77Ni0.25Se2And is denoted as CNSe-3.
Example 4: the preparation method of the nickel-doped cobalt selenide electro-catalytic hydrogen evolution catalyst comprises the following steps:
weighing 2.00mmol selenium powder and 1.0mmol Co (NO)3)2·6H2O, 1.00mmol of Ni (NO)3)2·6H2O, II, dissolving 2.00mmol selenium powder in 5mL potassium hydroxide solution with the concentration of 20mol/L, stirring for 30min, adding 1.0mmol Co (NO)3)2·6H2O, 1.00mmol of Ni (NO)3)2·6H2O, 1.60mmol of EDTA-2Na and 20mL of ultrapure water, and continuously stirring for about 1-1.5 h to obtain a mixed solution;
thirdly, transferring the mixture into a Teflon reaction kettle, reacting for 12 hours at the temperature of 180 ℃, and naturally cooling to room temperature;
fourthly, washing the black precipitate obtained by the reaction with water and ethanol for 3 times respectively, and then placing the black precipitate in a vacuum oven at 65 ℃ for 12 hours to obtain the nickel-doped cobalt selenide electro-catalysis hydrogen evolution catalyst, wherein the chemical formula of the catalyst is Co0.61Ni0.31Se2And is denoted as CNSe-4.
Comparative example 1: the catalyst of this example is not doped with Ni, and the specific preparation method is performed according to the following steps:
firstly, dissolving 2.00mmol selenium powder in 5mL potassium hydroxide solution with the concentration of 20mol/L, stirring for 30min, and then adding 1.0mmol Co (NO)3)2·6H2O, 1.60mmol of EDTA-2Na and 20mL of ultrapure water, and continuously stirring for about 1-1.5 h to obtain a mixed solution;
secondly, transferring the mixture into a Teflon reaction kettle, reacting for 12 hours at the temperature of 180 ℃, and naturally cooling to room temperature;
thirdly, washing the black precipitate obtained by the reaction with water and ethanol for 3 times respectively, and then placing the black precipitate in a vacuum oven at 65 ℃ for 12 hours to obtain a catalyst CoSe2。
Comparative example 2: the catalyst of this example was prepared without addition of Co, using the following procedure:
firstly, dissolving 2.00mmol selenium powder in 5mL potassium hydroxide solution with the concentration of 20mol/L, stirring for 30min, and then adding 2.00mmol Ni (NO)3)2·6H2O, 1.60mmol of EDTA-2Na and 20mL of ultrapure water, and continuously stirring for about 1-1.5 h to obtain a mixed solution;
secondly, transferring the mixture into a Teflon reaction kettle, reacting for 12 hours at the temperature of 180 ℃, and naturally cooling to room temperature;
thirdly, washing the black precipitate obtained by the reaction with water and ethanol for 3 times respectively, and then placing the black precipitate in a vacuum oven at 65 ℃ for 12 hours to obtain a catalyst NiSe2。
Materials CNSe-1, CNSe-2, CNSe-3, CNSe-4 and CoSe prepared in examples 1 to 4 and comparative examples 1 to 22And NiSe2Electrochemical tests were performed to obtain a polarization curve as shown in FIG. 1, a Tafel slope as shown in FIG. 2, an overpotential histogram as shown in FIG. 3, a Tafel slope histogram as shown in FIG. 4,
as can be seen from FIG. 1, the overpotentials (current density of 10mA cm) of CNSe-1, CNSe-2, CNSe-3, and CNSe-4-2The potential of cobalt selenide and nickel selenide in pure phase), especially the overpotential of CNSe-3 is as low as-172 mV, which is better than that of most transition metal chalcogenide compounds.
As can be seen from FIG. 2, the Tafel slope of CNSe-3 is the lowest, about 32.4mV dec–130.7mV dec, slightly greater than commercial platinum carbon–1Thus, the catalytic activity is higher.
As can be seen from fig. 3, after the nickel element is introduced into the cobalt selenide, the overpotential of all doped samples is reduced, the overall change is in a V shape, the nickel doping amount in CNSe-3 is the optimal value, and after the nickel is doped into the cobalt selenide, defects are formed on the cobalt selenide base surface, so that the active sites of the composite material are increased, and the catalytic activity is enhanced.
As can be seen from FIG. 4, the Tafel slope distribution trend of all samples was similar to the overpotential, again confirming that the amount of nickel doping in CNSe-3 was the optimum.
Example 3 preparation of a compound of formula Co0.77Ni0.25Se2The continuous cyclic voltammetry curve of the catalyst CNSe-3 is shown in figure 5, after 1,000 cycles of the continuous cyclic voltammetry test, the polarization curve almost coincides with the initial curve, and the current density does not change obviously under the overpotential condition for 10,000s, which indicates that the material also has ultrahigh stability.
Example 3 preparation of a compound of formula Co0.77Ni0.25Se2The 10,000s current density change curve of the catalyst CNSe-3 at a potential of-179 mV is shown in FIG. 6, and it can be seen from FIG. 6 that the current density of CNSe-3 in the 10000s chronopotentiometry test exhibits periodic changes, but is maintained at about 13mA cm overall-2Again, the stability of the sample was confirmed to be good.
Example 3 preparation of a compound of formula Co0.77Ni0.25Se2The scanning electron microscope photo of the catalyst CNSe-3 is shown in FIG. 7, and as can be seen from FIG. 7, the CNSe-3 is composed of nanosheets with uniform sizes of 200-300 nm, the structure is favorable for contact between electrolyte and the catalyst, bubbles generated by hydrolysis are easy to remove from the surface of the catalyst, the catalyst cannot fall off from the surface of a working electrode due to overlarge bubbles in the continuous electrocatalysis process, and the stability is improved.
Example 3 preparation of a compound of formula Co0.77Ni0.25Se2The transmission electron microscope photo of the catalyst CNSe-3 is shown in FIG. 8, and as can be seen from FIG. 8, the result is consistent with the scanning electron microscope test, and the sample consists of two-dimensional nano-sheets with the thickness of 200-300 nm.
The compositions of CNSe-1, CNSe-2, CNSe-3 and CNSe-4 obtained by the energy spectrum test are shown in Table 1.
TABLE 1 atomic percentages obtained by EDX spectroscopy
As can be seen from table 1, the atomic number ratio of nickel, cobalt and selenium elements in all the samples of nickel-doped cobalt selenide corresponds to the molecular formula.
Claims (6)
1. A nickel-doped cobalt selenide electro-catalysis hydrogen evolution catalyst is characterized in that the chemical general formula of the catalyst is CoxNiySe2Wherein x is 0.6-0.8, and y is 0.1-0.35.
2. The method for preparing the nickel-doped cobalt selenide electro-catalytic hydrogen evolution catalyst as claimed in claim 1, which is characterized by comprising the following steps:
one, press CoxNiySe2Weighing selenium powder and Co (NO) according to the stoichiometric ratio3)2·6H2O and Ni (NO)3)2·6H2O，CoxNiySe2Wherein x is 0.6-0.8, and y is 0.1-0.35; then weighing potassium hydroxide solution, EDTA-2Na and ultrapure water;
secondly, dissolving the selenium powder in a potassium hydroxide solution, stirring for 25-35 min, and adding Co (NO)3)2·6H2O、Ni(NO3)2·6H2O, EDTA-2Na and ultrapure water, and continuously stirring for about 1-1.5 h to obtain a mixed solution;
thirdly, transferring the mixture into a Teflon reaction kettle, reacting for 10-16 h at the temperature of 160-200 ℃, and naturally cooling to room temperature;
and fourthly, washing the black precipitate obtained by the reaction with water and ethanol in sequence, and then placing the black precipitate in a vacuum oven at the temperature of 60-65 ℃ for 12-15 hours to obtain the nickel-doped cobalt selenide electro-catalysis hydrogen evolution catalyst.
3. The preparation method of the nickel-doped cobalt selenide electro-catalytic hydrogen evolution catalyst as claimed in claim 2, wherein the concentration of the potassium hydroxide solution in the step one is 20-25 mol/L.
4. The method for preparing a nickel-doped cobalt selenide electro-catalytic hydrogen evolution catalyst according to claim 2 or 3, wherein the molar ratio of the selenium powder to the potassium hydroxide in the potassium hydroxide solution in the step one is 1: (50-60).
5. The method for preparing the nickel-doped cobalt selenide electro-catalytic hydrogen evolution catalyst according to claim 2 or 3, wherein the molar ratio of the selenium powder to the EDTA-2Na in the step one is 1: (0.8-0.9).
6. The method for preparing a nickel-doped cobalt selenide electro-catalytic hydrogen evolution catalyst as claimed in claim 2 or 3, wherein in the first step, the ratio of the amount of the selenium powder to the volume of the ultrapure water is 1 mmol: (10-12) mL.
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| CN114959780A (en) * | 2022-04-22 | 2022-08-30 | 中国石油大学(华东) | Core-shell structure cobalt-doped nickel diselenide electrocatalytic material and preparation method thereof |
| CN117107273A (en) * | 2023-08-21 | 2023-11-24 | 哈尔滨工业大学水资源国家工程研究中心有限公司 | Preparation method of zinc-doped cobalt selenide catalyst |
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| CN111514910A (en) * | 2020-06-17 | 2020-08-11 | 台州学院 | Co containing cobalt vacancy18Ni2Se20Compound (I) |
| CN111939945A (en) * | 2020-08-20 | 2020-11-17 | 安阳师范学院 | CoSe2NiSe2Preparation of-CC composite material and application of electrolytic water hydrogen evolution performance thereof |
| CN112481653A (en) * | 2020-10-29 | 2021-03-12 | 浙江大学衢州研究院 | Defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst and preparation method and application thereof |
| CN112481653B (en) * | 2020-10-29 | 2022-04-01 | 浙江大学衢州研究院 | Defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst and preparation method and application thereof |
| CN113604838A (en) * | 2021-08-17 | 2021-11-05 | 江苏大学 | Preparation method and application of nickel-cobalt bimetallic selenide heterostructure electrocatalyst |
| CN114959780A (en) * | 2022-04-22 | 2022-08-30 | 中国石油大学(华东) | Core-shell structure cobalt-doped nickel diselenide electrocatalytic material and preparation method thereof |
| CN117107273A (en) * | 2023-08-21 | 2023-11-24 | 哈尔滨工业大学水资源国家工程研究中心有限公司 | Preparation method of zinc-doped cobalt selenide catalyst |
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