CN114150341A - Transition metal selenide electrocatalytic material and preparation method and application thereof - Google Patents
Transition metal selenide electrocatalytic material and preparation method and application thereof Download PDFInfo
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- CN114150341A CN114150341A CN202111193513.5A CN202111193513A CN114150341A CN 114150341 A CN114150341 A CN 114150341A CN 202111193513 A CN202111193513 A CN 202111193513A CN 114150341 A CN114150341 A CN 114150341A
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 63
- -1 Transition metal selenide Chemical class 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 27
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 150000003624 transition metals Chemical class 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 description 14
- 229920000049 Carbon (fiber) Polymers 0.000 description 12
- 239000004917 carbon fiber Substances 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910052573 porcelain Inorganic materials 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- 239000011669 selenium Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 241000282414 Homo sapiens Species 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000009489 vacuum treatment Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
Images
Classifications
-
- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- 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 provides a transition metal selenide electrocatalytic material and a preparation method and application thereof, wherein the preparation method comprises the following steps: uniformly mixing a transition metal cation solution and a persulfate ion solution to obtain a mixed solution, putting a conductive substrate into the mixed solution, dripping ammonia water under a stirring state, standing, and taking out the conductive substrate to carry out primary calcination to obtain a precursor; and placing the precursor and selenium powder in a tubular furnace, and carrying out secondary calcination in an inert gas atmosphere or a reducing gas atmosphere to obtain the transition metal selenide electro-catalytic material. The invention prepares the precursor material by a solution method, and then obtains the transition metal selenide electrocatalytic material applied to electrocatalytic hydrogen evolution by a chemical vapor deposition selenizing method.
Description
Technical Field
The invention relates to the technical field of electrolytic water catalysis, in particular to a transition metal selenide electrocatalytic material and a preparation method and application thereof.
Background
With the advance of industrialization, fossil fuels bring convenience to human society and harm to human beings, and during the combustion process of the fossil fuels, COx, SOx, NOx and other gases which are not friendly to the environment are discharged, and the gases directly influence the living environment and the physical and mental health of human beings. In recent years, more and more scientists have focused their attention on hydrogen energy, which benefits from the fact that the combustion product is water only, achieving CO2The method has zero emission, and is clean and environment-friendly renewable energy.
In the existing hydrogen production technology, the method for preparing hydrogen by electrolyzing water has the advantages of high product purity, simple operation, no pollution of products, recycling and the like, so that people pay extensive attention to the method. Among them, the noble metal platinum Pt is a catalyst having the highest HER catalytic activity. However, since Pt is expensive and the earth content is insufficient, the production cost is greatly increased if it is used on a large scale.
In recent years, research on hydrogen production by water electrolysis has found that a transition metal compound with a nano structure can be a substitute for a noble metal such as Pt, and therefore how to develop a water electrolysis catalytic material by using a transition metal is a problem to be solved.
Disclosure of Invention
In view of the above, the invention provides a transition metal selenide electro-catalytic material, and a preparation method and an application thereof, so as to solve the problems that the existing electrolytic water catalytic material is expensive and is not suitable for large-scale popularization.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a transition metal selenide electrocatalytic material comprises the following steps:
s1, uniformly mixing the transition metal cation solution with the persulfate ion solution to obtain a mixed solution, putting the conductive substrate into the mixed solution, dripping ammonia water under a stirring state, standing, and taking out the conductive substrate for primary calcination to obtain a precursor;
and S2, placing the precursor and selenium powder in a tube furnace, and carrying out secondary calcination in an inert gas atmosphere or a reducing gas atmosphere to obtain the transition metal selenide electrocatalytic material.
Optionally, in step S1, the transition metal cation solution includes a transition metal-containing chloride salt, a transition metal-containing sulfate salt, or a transition metal-containing nitrate salt, the transition metal including one of iron, cobalt, and nickel; the sulfate ion solution comprises sodium persulfate and/or potassium persulfate; the conductive substrate includes one of fiber paper, foamed nickel, and foamed copper.
Alternatively, in step S1, the solution temperature is maintained in the range of 8 ℃ to 26 ℃ after dropping the ammonia water.
Alternatively, in step S1, the conditions of the first calcination include: the calcining temperature is in the range of 200 ℃ to 400 ℃ and the calcining time is in the range of 30min to 120 min.
Optionally, in step S2, the precursor and the selenium powder are placed in different temperature zones in the tube furnace.
Optionally, a temperature zone of the precursor is heated to 600 ℃ at a speed of 0.3-11.5 ℃/min for calcination, and the temperature is kept for 37-146 min; the temperature of the temperature zone where the selenium powder is positioned is raised to 400 ℃ at the speed of 0.1-10.8 ℃/min, and the temperature is kept for 37-146 min.
Optionally, the inert gas atmosphere or the reducing gas atmosphere comprises one of argon, helium, ammonia and a nitrogen-hydrogen mixed gas.
The second purpose of the invention is to provide a transition metal selenide electrocatalytic material, which is prepared by adopting the preparation method of the transition metal selenide electrocatalytic material.
The third purpose of the invention is to provide an application of the transition metal selenide electro-catalytic material in the field of electrolytic water catalysis.
Optionally, the transition metal selenide electrocatalytic material is used as a cathode material, and the use temperature is in the range of 5 ℃ to 65 ℃.
Compared with the prior art, the transition metal selenide electrocatalytic material and the preparation method and application thereof provided by the invention have the following advantages:
the transition metal selenide electro-catalytic material prepared by the invention has the advantages of high specific surface area, abundant active sites, high charge transmission capability, high activity and durability in strong base electrolyte, low cost, simple method, good idea and direction for preparing the electro-catalytic material and good application prospect.
Drawings
In order to more clearly illustrate the technical solutions of the present invention or the prior art, the drawings needed for the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and those skilled in the art can also obtain other drawings according to the drawings without creative efforts.
FIG. 1 is an XRD pattern of a transition metal selenide electrocatalytic material described in embodiments 1-3 of the present invention;
FIG. 2 is a hydrogen evolution polarization curve for the transition metal selenide electrocatalytic materials described in examples 1-3 of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
It should be noted that in the description of the embodiments herein, the description of the term "some embodiments" means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. Throughout this specification, the schematic representations of the terms used above do not necessarily refer to the same implementation or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The term "in.. range" as used herein includes both ends, such as "in the range of 1 to 100" including both ends of 1 and 100.
The embodiment of the invention provides a preparation method of a transition metal selenide electrocatalytic material, which comprises the following steps:
s1, uniformly mixing the transition metal cation solution and the persulfate ion solution to obtain a mixed solution, putting the conductive substrate into the mixed solution, dripping ammonia water under a constant-temperature stirring state, keeping the temperature within the range of 8-26 ℃, standing, taking out the conductive substrate, washing 1-5 times with deionized water, drying, and then carrying out primary calcination to obtain a precursor;
and S2, placing the precursor and selenium powder in a tube furnace, and carrying out secondary calcination in an inert gas atmosphere or a reducing gas atmosphere to obtain the transition metal selenide electrocatalytic material.
Specifically, in step S1, the transition metal cation solution includes a chloride containing transition metal, a sulfate containing transition metal, or a nitrate containing transition metal, and the transition metal includes one of iron, cobalt, and nickel.
Preferably, the transition metal cation solution includes one of ferric chloride, ferric sulfate, ferric nitrate, cobalt chloride, cobalt sulfate, cobalt nitrate, nickel chloride, nickel sulfate and nickel nitrate.
The sulfate ion solution comprises sodium persulfate and/or potassium persulfate; the conductive substrate includes one of fiber paper, nickel foam, and copper foam.
Wherein, the conditions of the first calcination of the conductive substrate comprise: the calcining temperature is in the range of 200 ℃ to 400 ℃ and the calcining time is in the range of 30min to 120 min.
Specifically, in step S2, during the preparation of the electrocatalytic material, the precursor and the selenium powder are placed in different temperature zones in the tube furnace. The selenium powder and the precursor in the single temperature zone are placed in the quartz tube and are flushed with the introduced air flow, the flow of selenium steam is influenced, the selenization degree is poor, the selenization in the double temperature zone is easier to control the concentration of the selenium steam, the problem of the stagnation of the flow of the selenium steam generated by the flushing of the introduced air flow and the selenium steam is solved, and the selenization reaction degree is improved.
Wherein the inert gas atmosphere or the reducing gas atmosphere comprises one of argon, helium, ammonia and nitrogen-hydrogen mixed gas.
Heating the temperature zone of the precursor to 600 ℃ at the speed of 0.3-11.5 ℃/min for calcination, and preserving the temperature for 37-146 min; the temperature of the temperature zone where the selenium powder is positioned is raised to 400 ℃ at the speed of 0.1-10.8 ℃/min, and the temperature is kept for 37-146 min.
Namely, the two temperature zones where the precursor and the selenium powder are located are simultaneously heated to the starting point of heat preservation, and the heat preservation time is kept consistent.
According to the embodiment of the invention, a precursor material is prepared by calcining through a solution method, and then the transition metal selenide electrocatalytic material is obtained through a chemical vapor deposition selenizing method. The transition metal selenide electrocatalytic material has high specific surface area, abundant active sites and high charge transmission capability, and has high activity and durability in strong base electrolyte. In addition, the preparation method is simple, low in cost and suitable for popularization.
Another embodiment of the present invention provides a transition metal selenide electrocatalytic material, which is prepared by the preparation method of the transition metal selenide electrocatalytic material.
The invention also provides application of the transition metal selenide electro-catalytic material in the field of electrolytic water catalysis. Wherein the transition metal selenide electrocatalytic material is used as a cathode material, and the use temperature is in the range of 5 ℃ to 65 ℃.
The transition metal selenide electrocatalytic material has high specific surface area, abundant active sites and high charge transmission capability, thereby showing excellent hydrogen evolution performance, providing better idea and direction for hydrogen production by water electrolysis and having good application prospect.
On the basis of the above embodiments, the present invention will be further illustrated by the following specific examples of the preparation method and application of the transition metal selenide electrocatalytic material. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are examples of experimental procedures not specified under specific conditions, generally according to the conditions recommended by the manufacturer. Unless otherwise indicated, percentages and parts are by mass.
Example 1
The embodiment provides a preparation method of a transition metal selenide electrocatalytic material, which comprises the following steps:
1) weighing 5g of nickel sulfate and potassium persulfate according to the mass ratio of 7:1, dissolving in 28mL of deionized water, and stirring for 10min at the temperature of 15 ℃; soaking the carbon fiber paper into the solution for 3min, dropwise adding 4mL of ammonia water, stirring the solution to be dark blue, standing for 20min, taking out the carbon fiber paper, washing the carbon fiber paper with deionized water for three times, and drying; and calcining the dried carbon fiber paper in air at 300 ℃ for 60min to obtain a precursor.
2) Weighing 0.5g of selenium powder, respectively placing the selenium powder and the precursor on two small porcelain boats, placing the porcelain boats in two different temperature zones of the same tube furnace, sealing the tube furnace for vacuum treatment, and introducing 8% nitrogen-hydrogen mixed gas for heating treatment to obtain the transition metal selenide electrocatalytic material. Wherein the temperature rise time of the temperature zone where the selenium powder is located is 75min, the heat preservation temperature is 350 ℃, and the heat preservation time is 60 min; the temperature rise time of the temperature zone of the precursor is 75min, the heat preservation temperature is 600 ℃, and the heat preservation time is 60 min.
Example 2
The embodiment provides a preparation method of a transition metal selenide electrocatalytic material, which comprises the following steps:
1) weighing 5g of nickel sulfate and potassium persulfate according to the mass ratio of 7:1, dissolving in 28mL of deionized water, and stirring for 10min at the temperature of 10 ℃; soaking the carbon fiber paper into the solution for 3min, dropwise adding 4mL of ammonia water, stirring the solution to be dark blue, standing for 20min, taking out the carbon fiber paper, washing the carbon fiber paper with deionized water for three times, and drying; and calcining the dried carbon fiber paper in air at 300 ℃ for 90min to obtain a precursor.
2) Weighing 0.5g of selenium powder, respectively placing the selenium powder and the precursor on two small porcelain boats, placing the porcelain boats in two different temperature zones of the same tube furnace, sealing the tube furnace for vacuum treatment, and introducing 8% nitrogen-hydrogen mixed gas for heating treatment to obtain the transition metal selenide electrocatalytic material. Wherein the temperature rise time of the temperature zone where the selenium powder is located is 100min, the heat preservation temperature is 375 ℃, and the heat preservation time is 50 min; the temperature rise time of the temperature zone of the precursor is 100min, the heat preservation temperature is 500 ℃, and the heat preservation time is 50 min.
Example 3
The embodiment provides a preparation method of a transition metal selenide electrocatalytic material, which comprises the following steps:
1) weighing 5g of nickel sulfate and potassium persulfate according to the mass ratio of 7:1, dissolving in 28mL of deionized water, and stirring for 10min at the temperature of 20 ℃; soaking the carbon fiber paper into the solution for 3min, dropwise adding 4mL of ammonia water, stirring the solution to be dark blue, standing for 20min, taking out the carbon fiber paper, washing the carbon fiber paper with deionized water for three times, and drying; and calcining the dried carbon fiber paper in air at 300 ℃ for 45min to obtain a precursor.
2) Weighing 0.5g of selenium powder, respectively placing the selenium powder and the precursor on two small porcelain boats, placing the porcelain boats in two different temperature zones of the same tube furnace, sealing the tube furnace for vacuum treatment, and introducing 8% nitrogen-hydrogen mixed gas for heating treatment to obtain the transition metal selenide electrocatalytic material. Wherein the temperature rise time of the temperature zone where the selenium powder is located is 40min, the heat preservation temperature is 325 ℃, and the heat preservation time is 80 min; the temperature rise time of the temperature zone of the precursor is 40min, the heat preservation temperature is 400 ℃, and the heat preservation time is 80 min.
The transition metal selenide electrocatalytic materials prepared in examples 1 to 3 were subjected to phase characterization and hydrogen evolution performance test using an X-ray diffractometer (XRD), using an LSV method, with a voltage range of-1.03V to-1.5V, 1M KOH solution as an electrolyte, and a sweep rate of 5mVs-1The results are shown in FIGS. 1 and 2.
As can be seen from FIG. 1, the transition metal selenide electrocatalytic materials prepared in examples 1 to 3 are all NiSe2。
As can be seen from fig. 2, the transition metal selenide electrocatalytic materials prepared in examples 1 to 3 have better performance, wherein the overpotential is smaller at a high current density when the selenization temperature is 500 ℃.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.
Claims (10)
1. A preparation method of a transition metal selenide electrocatalytic material is characterized by comprising the following steps:
s1, uniformly mixing the transition metal cation solution with the persulfate ion solution to obtain a mixed solution, putting the conductive substrate into the mixed solution, dripping ammonia water under a stirring state, standing, and taking out the conductive substrate for primary calcination to obtain a precursor;
and S2, placing the precursor and selenium powder in a tube furnace, and carrying out secondary calcination in an inert gas atmosphere or a reducing gas atmosphere to obtain the transition metal selenide electrocatalytic material.
2. The method according to claim 1, wherein in step S1, the transition metal cation solution includes a transition metal-containing chloride salt, a transition metal-containing sulfate salt, or a transition metal-containing nitrate salt, the transition metal including one of iron, cobalt, and nickel; the sulfate ion solution comprises sodium persulfate and/or potassium persulfate; the conductive substrate includes one of fiber paper, foamed nickel, and foamed copper.
3. The production method according to claim 2, wherein in step S1, the temperature of the solution is maintained within a range of 8 ℃ to 26 ℃ after dropping of the aqueous ammonia.
4. The method according to claim 2, wherein in step S1, the conditions of the first calcination include: the calcining temperature is in the range of 200 ℃ to 400 ℃ and the calcining time is in the range of 30min to 120 min.
5. The method according to any one of claims 1 to 4, wherein the precursor and the selenium powder are placed in different temperature zones in the tube furnace in step S2.
6. The preparation method according to claim 5, characterized in that the temperature zone of the precursor is heated to 600 ℃ at the rate of 0.3-11.5 ℃/min for calcination and is kept for 37-146 min; the temperature of the temperature zone where the selenium powder is positioned is raised to 400 ℃ at the speed of 0.1-10.8 ℃/min, and the temperature is kept for 37-146 min.
7. The method of claim 5, wherein the inert gas atmosphere or the reducing gas atmosphere comprises one of argon, helium, ammonia, and a mixed gas of nitrogen and hydrogen.
8. A transition metal selenide electrocatalytic material, characterized by being prepared by the method for preparing the transition metal selenide electrocatalytic material as described in any one of claims 1 to 7.
9. The use of the transition metal selenide electrocatalytic material as claimed in claim 8 in the field of electrolytic water catalysis.
10. Use according to claim 9, wherein the transition metal selenide electrocatalytic material is used as a cathode material at a temperature in the range of 5 ℃ to 65 ℃.
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