CN115198304B - Nickel selenide sulfide composite seawater electrocatalyst and preparation method and application thereof - Google Patents
Nickel selenide sulfide composite seawater electrocatalyst and preparation method and application thereof Download PDFInfo
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- 239000013535 sea water Substances 0.000 title claims abstract description 45
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 42
- IRLJWYDLXZTYRE-UHFFFAOYSA-N [Se].[S].[Ni] Chemical compound [Se].[S].[Ni] IRLJWYDLXZTYRE-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000013099 nickel-based metal-organic framework Substances 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 50
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000004523 catalytic cracking Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229940075397 calomel Drugs 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 10
- 238000005336 cracking Methods 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003346 selenoethers Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- QVYIMIJFGKEJDW-UHFFFAOYSA-N cobalt(ii) selenide Chemical compound [Se]=[Co] QVYIMIJFGKEJDW-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- -1 transition metal selenides Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- 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
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- 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
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- 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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
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- C25B11/031—Porous electrodes
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- 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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
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- 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
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a nickel selenide sulfide composite seawater electrocatalyst, a preparation method and application thereof, and belongs to the field of catalysts 2 The structure of the NiSSe is a sheet structure, and the thickness of the NiSSe is 5-10 nm. The preparation method comprises the following steps: preparing a transparent solution; (2) preparation of Ni-MOF/NF precursor; (3) NiSe 2 Preparation of NiSSe electrocatalyst. The invention also discloses application of the nickel selenide sulfide composite seawater electrocatalyst in hydrogen production by electrocatalysis cracking seawater. NiSe prepared by the invention 2 The NiSSe electrocatalyst has the characteristics of large specific surface area, high activity and high stability, and has excellent hydrogen production performance in alkaline seawater. In addition, the preparation method provided by the invention has the advantages of mild conditions, simple operation and strong repeatability, and provides good technical basis and material guarantee for large-area application.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a nickel selenide sulfide composite seawater electrocatalyst and a preparation method and application thereof.
Background
Hydrogen energy has received wide attention in recent years, and electrocatalysis cracking water for hydrogen production, especially electrocatalysis cracking seawater provides an effective means for solving energy crisis and developing new energy. In recent years, the design of electrocatalyst materials, particularly noble metal materials (e.g., platinum, iridium), have been extensively studied for their excellent hydrogen sorption capabilities. However, it has not been developed rapidly due to problems such as high price and low storage capacity.
In the conventional transition metal materials, transition metal selenides such as nickel selenide, cobalt selenide and the like have abundant reserves and adjustable electronic structures, and are considered to have the potential of replacing platinum-based noble metal catalysts in the field of hydrogen production by electrocatalysis. However, the current use of less active sites due to their poor conductivity limits their performance in the electrocatalytic cracking of water to produce hydrogen. In the prior art, reports about selenide multi-component doping are few, related tests on the performance of electro-catalytic cracking seawater are not carried out, and a large improvement space still exists in the aspects of synthesis methods, design strategies and the like.
Therefore, how to provide an economic and efficient electrocatalyst to promote the rapid development of selenide-based materials in the field of electrocatalytic cracking of seawater and finally realize industrialization thereof is a technical problem which needs to be solved by the technical personnel in the field.
Disclosure of Invention
The invention aims to provide a nickel selenide sulfide composite seawater electrocatalyst with a flaky structure, a large specific surface area, and high activity and stability, and a preparation method and application thereof, so as to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following scheme:
a nickel selenide sulfide composite seawater electrocatalyst with a molecular formula of NiSe 2 The structure of the NiSSe is a sheet structure, and the thickness of the NiSSe is 5-10 nm.
Has the advantages that: the electronic structure of the nickel selenide material can be optimized by doping the nonmetal, so that the synergistic effect is exerted, and the transfer speed of electrons is accelerated. Water molecules in the seawater are adsorbed on the surface of the catalyst, and the water molecules obtain electrons to generate hydrogen protons. Subsequently, the two hydrogen protons combine to generate hydrogen gas.
A preparation method of a nickel selenide sulfide composite seawater electrocatalyst comprises the following steps:
(1) Dropwise adding a terephthalic acid solution into a nickel chloride hexahydrate solution, and continuously stirring to obtain a transparent solution;
(2) Adding foamed nickel into the transparent solution, standing for 5-10 min, reacting at 50-150 ℃ for 10-24 h, cooling to room temperature, and washing and vacuum drying solid products in sequence to obtain a Ni-MOF/NF precursor;
(3) Adding selenium powder and sulfur powder into the Ni-MOF/NF precursor, and reacting for 0.5-5 h at 300-700 ℃ to obtain black NiSe 2 A NiSSe electrocatalyst.
Has the advantages that: niSe 2 the/NiSSe electrocatalyst has a flaky nano structure, can provide rich specific surface area, and further improves the catalytic activity of the catalyst.
Preferably, the terephthalic acid solution in the step (1) is prepared by dissolving terephthalic acid in a mixed solution of deionized water, N, N-dimethylformamide and ethanol;
the addition ratio of the terephthalic acid to the deionized water to the N, N-dimethylformamide to the ethanol is 5:1:16:1.
preferably, the concentration of the nickel chloride hexahydrate solution is 0.01-0.10 mol/L;
the mass ratio of the cobalt chloride hexahydrate to the terephthalic acid is 1 (0.1-5.0).
Has the advantages that: the raw materials provide a nickel source and an organic ligand for the synthesis of Ni-MOF.
Preferably, the thickness of the foamed nickel in the step (2) is 1.5mm, and the area of the foamed nickel is 1-4 cm 2 。
Has the advantages that: the foamed nickel in the invention provides a substrate for Ni-MOF/NF.
Preferably, in the step (2), the vacuum drying temperature is 5-100 ℃, the drying time is 8-72 h, and the vacuum degree is 133-267 Pa.
Has the advantages that: the above conditions provide a vacuum drying environment, which is beneficial to drying the sample.
Preferably, the area of the Ni-MOF/NF precursor in the step (2) is 1-4 cm 2 。
Has the advantages that: providing a precursor for selenization.
Preferably, the mass ratio of the Ni-MOF/NF precursor, the sulfur powder and the selenium powder in the step (2) is 1:1 (0.1-5.0).
Has the advantages that: the raw materials provide a selenium source and a sulfur source for the preparation of the electrocatalyst.
An application of a nickel selenide sulfide composite seawater electrocatalyst in the electro-catalytic cracking of seawater to produce hydrogen.
Has the advantages that: the catalyst obtained by the test of the invention has the performance of producing hydrogen by electrocatalytic cracking of seawater.
Preferably, the NiSe 2 the/NiSSe is a working electrode; a calomel electrode is used as a reference electrode; the graphite electrode is used as a counter electrode; the electrolyte is alkaline seawater, and can also be alkaline simulated seawater or KOH solution; the pH value of the electrolyte is 10-14.
Preferably, the seawater is alkaline seawater (KOH + true seawater), wherein the seawater is obtained from yellow sea of China, and the concentration of KOH is 1.0mol/L.
Has the advantages that: the above conditions are the conditions for testing the electro-catalytic cracking of seawater by the electro-catalyst and the source of seawater.
The invention discloses a nickel selenide sulfide composite seawater electrocatalyst, a preparation method and application thereof, and NiSe prepared by the invention 2 The NiSSe electrocatalyst has the characteristics of large specific surface area, high activity and high stability, and has excellent hydrogen production performance in alkaline seawater. Further, niSe in the present invention 2 The NiSSe electrocatalyst has the advantages of mild preparation conditions, simple operation, strong repeatability and low requirements on instruments and equipment, and provides good technical basis and material guarantee for large-area application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 is a scanning electron microscope image of the Ni-MOF/NF electrocatalyst prepared in example 1;
FIG. 2 is NiSe prepared in example 1 2 An X-ray diffraction spectrum of the NiSSe electrocatalyst;
FIG. 3 is NiSe prepared in example 1 2 Scanning electron microscopy images of/NiSSe electrocatalysts;
FIG. 4 is a drawing showingNiSe prepared in example 1 2 A performance diagram of cracking seawater to produce hydrogen by a NiSSe electrocatalyst in alkaline seawater.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
Example 1
NiSe 2 A preparation method of the NiSSe electrocatalyst comprises the following steps:
(1) Dispersing nickel chloride hexahydrate in deionized water at room temperature to obtain a pink transparent nickel chloride hexahydrate solution, wherein the concentration of the nickel chloride hexahydrate is 0.015mol/L;
(2) At room temperature, dissolving terephthalic acid in a mixed solution of deionized water, N, N-dimethylformamide and ethanol to ensure that the concentration of the terephthalic acid is 0.02mol/L, and obtaining a colorless and transparent terephthalic acid solution, wherein the volume ratio of the deionized water, the N, N-dimethylformamide and the ethanol is 1:16:1;
(3) Dropwise adding the terephthalic acid solution obtained in the step (2) into the nickel chloride hexahydrate solution obtained in the step (1), and continuously stirring to obtain a green transparent solution; wherein the mass ratio of the terephthalic acid to the nickel chloride hexahydrate in the step (1) is 1;
(4) The thickness is 1.5mm, and the area is 2cm 2 Adding the foamed nickel into the transparent solution obtained in the step (3), standing for 5min, transferring into a reaction kettle, reacting for 10h at 110 ℃ to obtain a foamed nickel material, fully washing with deionized water and ethanol, and performing vacuum drying to obtain the foamed nickel material with the area of 2cm 2 Ni-MOF/NF precursor of (A)A body;
(5) 2cm of the residue obtained in step (4) 2 Putting the Ni-MOF/NF precursor into a crucible, and adding selenium powder and sulfur powder into the crucible, wherein the mass ratio of the Ni-MOF/NF precursor to the selenium powder to the sulfur powder is 1:1:1;
(6) Transferring the crucible in the step (5) into a tube furnace, and reacting for 2h at 500 ℃ to obtain black NiSe 2 a/NiSSe electrocatalyst.
As can be seen from the scanning electron microscopy image of the prepared Ni-MOF/NF in FIG. 1, ni-MOF nanosheets grow on the nickel foam;
as can be seen from the powder X-ray diffraction spectrum of FIG. 2, the chemical composition of the prepared product is NiSe 2 And NiSSe;
subsequent scanning electron microscopy of FIG. 3 yields NiSe 2 the/NiSSe catalyst sample has good uniformity and is of a sheet structure.
Example 2
NiSe 2 A preparation method of the NiSSe electrocatalyst comprises the following steps:
(1) Dispersing nickel chloride hexahydrate in deionized water at room temperature to obtain a pink transparent nickel chloride hexahydrate solution, wherein the concentration of the nickel chloride hexahydrate is 0.015mol/L;
(2) At room temperature, terephthalic acid was dissolved in a mixed solution of deionized water, N-dimethylformamide and ethanol so that the concentration of terephthalic acid was 0.02mol/L. Obtaining a colorless and transparent terephthalic acid solution, wherein the volume ratio of the deionized water to the N, N-dimethylformamide to the ethanol is 1:16:1;
(3) Dropwise adding the terephthalic acid solution obtained in the step (2) into the nickel chloride hexahydrate solution obtained in the step (1), and continuously stirring to obtain a green transparent solution; wherein the mass ratio of the terephthalic acid to the nickel chloride hexahydrate in the step (1) is 1;
(4) The thickness is 1.5mm, and the area is 2cm 2 Adding the foamed nickel into the transparent solution obtained in the step (3), standing for 5min, transferring into a reaction kettle, reacting for 10h at 110 ℃ to obtain a foamed nickel material, fully washing with deionized water and ethanol, and carrying outVacuum drying to obtain area of 2cm 2 Ni-MOF/NF precursor of (a);
(5) 2cm of the mixture obtained in the step (4) 2 Putting the Ni-MOF/NF precursor into a crucible, and adding selenium powder and sulfur powder into the crucible, wherein the mass ratio of the Ni-MOF/NF precursor to the selenium powder to the sulfur powder is 1:1:1;
(6) Transferring the crucible in the step (5) into a tube furnace, and reacting for 2h at the temperature of 300 ℃ to obtain black NiSe 2 a/NiSSe electrocatalyst.
Example 3
NiSe 2 A preparation method of the NiSSe electrocatalyst comprises the following steps:
(1) Dispersing nickel chloride hexahydrate in deionized water at room temperature to obtain a pink transparent nickel chloride hexahydrate solution, wherein the concentration of the nickel chloride hexahydrate is 0.015mol/L;
(2) At room temperature, terephthalic acid was dissolved in a mixed solution of deionized water, N-dimethylformamide and ethanol so that the concentration of terephthalic acid was 0.02mol/L. Obtaining a colorless and transparent terephthalic acid solution, wherein the volume ratio of the deionized water to the N, N-dimethylformamide to the ethanol is 1:16:1;
(3) Dropwise adding the terephthalic acid solution obtained in the step (2) into the nickel chloride hexahydrate solution obtained in the step (1), and continuously stirring to obtain a green transparent solution, wherein the mass ratio of the terephthalic acid to the nickel chloride hexahydrate in the step (1) is 1;
(4) The thickness is 1.5mm, and the area is 2cm 2 Adding the foamed nickel into the transparent solution obtained in the step (3), standing for 5min, transferring into a reaction kettle, reacting for 10h at 110 ℃ to obtain a foamed nickel material, fully washing with deionized water and ethanol, and performing vacuum drying to obtain the foamed nickel material with the area of 2cm 2 Ni-MOF/NF precursor of (a);
(5) 2cm of the residue obtained in step (4) 2 Putting the Ni-MOF/NF precursor into a crucible, and adding selenium powder and sulfur powder into the crucible, wherein the mass ratio of the Ni-MOF/NF precursor to the selenium powder to the sulfur powder is 1:1:1;
(6) Transferring the crucible in the step (5) into a tube furnace,reacting for 2 hours at 700 ℃ to obtain black NiSe 2 A NiSSe electrocatalyst.
And (3) performance testing:
examples 1 to 3
NiSe 2 Application of NiSSe electrocatalyst in seawater cracking hydrogen production:
(1) Mixing NiSe 2 The NiSSe is directly used as a working electrode; a calomel electrode is used as a reference electrode; the graphite electrode is used as a counter electrode;
(2) The electrolyte tested in examples 1-4 was alkaline seawater (KOH + real seawater), wherein the real seawater was taken from the yellow sea of China, and the concentration of KOH was 1.0mol/L. The test results are shown in table 1.
TABLE 1NiSe 2 Electrocatalytic performance of NiSSe electrocatalyst
| Example 1 | Example 2 | Example 3 | |
| Overpotential | 125mV@30mAcm -2 | 200mV@30mAcm -2 | 180mV@30mAcm -2 |
As can be seen from Table 1 above, niSe 2 The NiSSe has excellent performance of producing hydrogen by electrically catalyzing and cracking seawater at 500 ℃, and is shown in figure 4.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (9)
1. The nickel selenide sulfide composite seawater electrocatalyst is characterized in that the chemical composition of the nickel selenide sulfide composite seawater electrocatalyst is NiSe 2 The structure of the NiSSe is a sheet structure, and the thickness of the NiSSe is 5-10 nm.
2. A method for preparing the nickel selenide sulfide composite seawater electrocatalyst according to claim 1, which comprises the following steps:
(1) Dropwise adding a terephthalic acid solution into a nickel chloride hexahydrate solution, and continuously stirring to obtain a transparent solution;
(2) Adding foamed nickel into the transparent solution, standing for 5-10 min, reacting at 50-150 ℃ for 10-24 h, cooling to room temperature, and sequentially washing and vacuum-drying solid products to obtain a Ni-MOF/NF precursor;
(3) Adding selenium powder and sulfur powder into the Ni-MOF/NF precursor, and reacting for 0.5-5 h at 300-700 ℃ to obtain black NiSe 2 a/NiSSe electrocatalyst.
3. The method for preparing the nickel selenide sulfide composite seawater electrocatalyst according to claim 2, wherein the terephthalic acid solution in the step (1) is prepared by dissolving terephthalic acid in a mixed solution of deionized water, N-dimethylformamide and ethanol;
the addition ratio of the terephthalic acid to the deionized water to the N, N-dimethylformamide to the ethanol is 5:1:16:1.
4. the method for preparing the nickel selenide sulfur composite seawater electrocatalyst according to claim 2, wherein the concentration of the nickel chloride hexahydrate in step (1) is 0.01-0.10 mol/L;
the mass ratio of the nickel chloride hexahydrate to the terephthalic acid is 1 (0.1-5.0).
5. The preparation method of the nickel selenide sulfide composite seawater electrocatalyst according to claim 2, wherein in the step (2), the thickness of the foamed nickel is 1.5mm, and the area of the foamed nickel is 1-4 cm 2 。
6. The preparation method of the nickel selenide sulfide composite seawater electrocatalyst according to claim 2, wherein the vacuum drying temperature in step (2) is 5-100 ℃, the drying time is 8-72 h, and the vacuum degree is 133-267 Pa.
7. The preparation method of the nickel selenide sulfide composite seawater electrocatalyst according to claim 2, wherein the mass ratio of the Ni-MOF/NF precursor, the sulfur powder and the selenium powder in the step (2) is 1:1 (0.1-5.0).
8. The application of the nickel selenide sulfide composite seawater electrocatalyst in claim 1 in the electro-catalytic cracking of seawater to produce hydrogen.
9. Use according to claim 8, wherein the NiSe is formed 2 The NiSSe is used as a working electrode; a calomel electrode is used as a reference electrode; the graphite electrode is used as a counter electrode; the electrolyte is alkaline seawater; the pH value of the electrolyte is 10-14.
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