CN111359637A - Hydrogen production catalyst nickel diselenide nanoparticle @ carbon nanosheet composite material and preparation method and application thereof - Google Patents
Hydrogen production catalyst nickel diselenide nanoparticle @ carbon nanosheet composite material and preparation method and application thereof Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 239000002135 nanosheet Substances 0.000 title claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000001257 hydrogen Substances 0.000 title claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- IJUKXQRCJABGNO-UHFFFAOYSA-N [Se].[Ni]=[Se] Chemical compound [Se].[Ni]=[Se] IJUKXQRCJABGNO-UHFFFAOYSA-N 0.000 title abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 22
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 claims abstract description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 13
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims abstract description 7
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 5
- 238000009792 diffusion process Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- 229920000557 Nafion® Polymers 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003346 selenoethers Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002055 nanoplate Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/23—
-
- B01J35/33—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
The invention discloses a nickel diselenide nanoparticle @ carbon nanosheet composite material as a hydrogen production catalyst, and a preparation method and application thereof, and belongs to the field of catalytic materials. The method comprises the steps of 1) dissolving divalent nickel salt, citric acid and urea into water together, evaporating the obtained solution to form gel, and carbonizing/reducing the gel at high temperature in a tubular furnace to form the Ni/C composite material; 2) the Ni/C composite material and selenium powder are subjected to gas phase diffusion combination reaction in a tubular furnace in a specific wayAt a temperature of (2) to obtain NiSe2Nanoparticle @ carbon nanosheet composites. The invention firstly takes simple substance nickel/carbon material with controllable carbon content as raw material to prepare NiSe with controllable carbon content by a controlled selenization method2The nano particle @ carbon nanosheet composite material is an optimized material for an electrolytic hydrogen production catalyst, and shows good catalytic activity. The method is simple, safe and efficient, and realizes controllable phase composition.
Description
Technical Field
The invention belongs to the field of catalytic materials, and particularly relates to a nickel diselenide nanoparticle @ carbon nanosheet composite material as a hydrogen production catalyst, and a preparation method and application thereof.
Background
Due to the characteristics of high energy density, no pollution, renewability and the like, hydrogen energy is an important component of future energy sources. The preparation of hydrogen by electrocatalytic decomposition of water is a convenient and efficient process. Water splitting mainly involves two half-reactions: the Oxygen Evolution Reaction (OER) at the anode reacts with the Hydrogen Evolution Reaction (HER) at the cathode. However, during the decomposition process, polarization, especially electrochemical polarization, can generate a relatively large overpotential, which seriously affects the efficiency and practical application of the water electrolysis.
The overpotential in the electrolytic process can be effectively reduced and the water decomposition efficiency can be improved by introducing a high-efficiency electrocatalyst, wherein the classical HER catalyst is rare noble metal oxide RuO2However, RuO2The problems of high cost and low reserve exist, and the large-scale application is difficult. The development of inexpensive, common HER catalysts has become one of the hot spots in electrocatalyst research. For example, transition metals with reasonable d-electron structures are the primary replacement elements for Ru, and reported transition metal compounds include oxides, hydroxides, sulfides, nitrides, and the like; the selenide has the optimal intrinsic conductivity, so that the HER performance of the material is better. Selenides are of various types, and NiSe is commonx、FeSexAnd CoSex，NiSe2Is a selenide which is widely researched and is used for constructing NiSe2In the case of electrocatalysts, there are 2 technical problems: (1) to increase NiSe2Specific surface area of (2), NiSe2The nano particles are designed and prepared, but the nano particles are easy to agglomerate due to larger surface energy, thereby preventing NiSe2Agglomeration is a technical key among them. (2) To inhibit NiSe2While improving stability, in the preparation of NiSe2By addition of a carbon-based substrateHowever, carbon substrate is difficult to be bonded with NiSe2Efficient binding and how efficiently the carbon content is controlled and optimized.
Disclosure of Invention
In order to solve the technical problem, the invention provides a hydrogen production catalyst NiSe2Nanoparticle @ carbon nanosheet composite material and preparation method thereof, and NiSe can be effectively and controllably prepared by the method2Nanoparticle @ carbon nanosheet composite, NiSe2Presents a nano-particle structure and is dispersed in a reasonable amount of carbon, thereby improving the performance of the catalyst as an electrochemical hydrogen production catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
NiSe2The preparation method of the nanoparticle @ carbon nanosheet composite material comprises the following steps:
1) dissolving a divalent nickel salt, citric acid and urea into deionized water, evaporating the obtained solution to form gel, and carbonizing/reducing the gel at high temperature in a tubular furnace to form a Ni/C composite material;
2) the Ni/C composite material and selenium powder are subjected to gas phase diffusion combination reaction in a tubular furnace to obtain NiSe at a specific temperature2Nanoparticle @ carbon nanosheet composites.
In the step 1), the divalent nickel salt is nickel nitrate or ferric chloride.
In the step 1), the mass ratio of the divalent nickel salt to the citric acid to the urea is 0.2:1:5 to 1:1: 5.
In the step 1), the evaporation is carried out for 4 to 5 hours at the temperature of 80 to 85 ℃.
In the step 1), the carbonization temperature is 500-800 ℃.
In the step 2), the mass ratio of the Ni/C composite material to the selenium powder is 1:5 to 1:20 so as to realize NiSe2And inhibit disproportionation or further combination thereof.
In the step 2), the Ni/C composite material and the selenium powder are placed in a tube furnace, the temperature in the tube furnace is raised to 400-600 ℃ at the heating rate of 5 ℃/min, and then the heat treatment is carried out for 2-4h at the temperature of 400-600 ℃ to obtain the NiSe2Nanoparticle @ carbon nanosheetA composite material.
NiSe provided by the invention2The nano particle @ carbon nano composite material is used for manufacturing a hydrogen production catalyst electrode and comprises the following steps:
1) mixing NiSe2Dispersing the nanoparticle @ carbon nanosheet composite material into ethanol, adding a 5wt% Nafion solution, and performing ultrasonic dispersion to form a relatively stable suspension;
2) and (3) dripping the suspension liquid on a rotating disk electrode, drying at a proper temperature to form an electrode, and performing performance test by using a three-electrode system.
In step 1), NiSe2The mass of the composite material is preferably 20-60mg, and the dosage of the Nafion solution is preferably 40-80 muL.
In step 2), the drying temperature of the suspension on the disk electrode is preferably 40 to 60 ℃.
According to the technical scheme, compared with the prior art, the hydrogen production catalyst NiSe provided by the invention2Preparation method of nanoparticle @ carbon nanosheet composite material, and application of composite material in electrochemical hydrogen production catalyst due to NiSe2The nano particles with good dispersion are dispersed in a proper amount of carbon substrate, thereby being beneficial to the performance of the catalyst as hydrogen production catalyst and simultaneously realizing the NiSe2And optimizing the ratio of carbon.
The invention firstly takes simple substance nickel/carbon material with controllable carbon content as raw material to prepare NiSe with controllable carbon content by a controlled selenization method2The nano particle @ carbon nanosheet composite material is an optimized material for an electrolytic hydrogen production catalyst, and shows good catalytic activity. The method is simple, safe and efficient, and realizes controllable phase composition.
The invention has the beneficial effects that: using optimized NiSe2Nanoparticle @ carbon nanoplate composites in solution at pH 0.3 at 10mA/cm2The overpotential is only 0.18V at the current density of (2).
Drawings
In FIG. 1, (a) is an X-ray diffraction (XRD) pattern of a Ni/C composite material; (b) is NiSe2Of nanoparticle @ carbon nanosheet compositesAn X-ray diffraction (XRD) pattern;
FIG. 2 is a representation of NiSe in the present invention2Scanning Electron Microscope (SEM) images of nanoparticles @ carbon nanoplatelets;
FIG. 3 is a representation of NiSe in the present invention2Transmission Electron Microscopy (TEM) images of nanoparticles @ carbon nanoplatelets;
figure 4 is a hydrogen evolution polarization curve for a representative sample.
Detailed Description
Example 1
NiSe2The preparation method of the nanoparticle @ carbon nanosheet composite material comprises the following steps:
step (1): putting 5.0g of urea, 1.0g of citric acid and 0.6g of nickel chloride hexahydrate in a 500mL beaker, adding 150mL of ethanol and 50mL of deionized water into the beaker, stirring to form a uniform solution, preserving the temperature of the solution at 85 ℃ for evaporating for 4 hours to form gel, and carbonizing the gel at 700 ℃ for 4 hours to obtain the Ni/C composite material.
Step (2): respectively placing 0.05gNi/C composite material and 1g selenium powder in the step (1) in a corundum magnetic boat, paving the corundum magnetic boat as far as possible, transferring a sample into a tube furnace for high-temperature selenization reaction, heating the sample to 400 ℃ at the heating rate of 5 ℃/min in the argon environment, carrying out heat treatment for 4 hours at the temperature of 400 ℃, cooling the sample to room temperature, pouring the powder material into an agate mortar, and grinding the powder material to obtain NiSe2Nanoparticle @ carbon nanosheet composites.
Ni/C and NiSe prepared by the method2The crystal structure of/C is shown in FIG. 1(0.6-Ni/C and 0.6-NiSe)2/C), XRD diffraction peaks in the spectrogram are respectively matched with Ni/C and NiSe2the/C is completely consistent, no obvious impure phase is found, and the diffraction peak is relatively sharp, which indicates that the material has better crystallinity.
Referring to fig. 2a and 2b, as can be seen from fig. 2a, the material has a distinct sheet structure and is relatively curled, and the main structure should be carbon; as can be seen from FIG. 2b, there are many nanoparticles on the surface of these sheet structures, forming NiSe2Nanoparticle @ carbon nanosheet composites.
Micro-topography of materialsReferring to FIG. 3, FIG. 3a is a TEM photograph of a sample prepared in an example of the present invention, from which NiSe can be seen2The nano particles are well dispersed on the carbon nano sheet; from fig. 3b it can be seen that the size of the nanoparticles is around 100 nm and that there is less agglomeration.
Example 2
NiSe2The preparation method of the nanoparticle @ carbon nanosheet composite material comprises the following steps:
step (1): putting 5.0g of urea, 1.0g of citric acid and 0.4g of nickel chloride hexahydrate in a 500mL beaker, adding 150mL of ethanol and 50mL of deionized water into the beaker, stirring to form a uniform solution, preserving the temperature of the solution at 85 ℃ for evaporating for 4 hours to form gel, and carbonizing the gel at 700 ℃ for 4 hours to obtain the Ni/C composite material.
Step (2): fully mixing 0.1g of the Ni/C composite material prepared in the previous step with 0.5g of selenium powder, reacting for 2 hours in a 500 ℃ tube furnace under the argon atmosphere, cooling to room temperature, pouring the powder material into an agate mortar, and grinding to obtain NiSe2Nanoparticle @ carbon nanosheet composites.
NiSe prepared by the method2The crystal structure of the nanoparticle @ carbon nanosheet composite material is shown in FIG. 1(0.4-Ni/C and 0.4-NiSe)2/C), XRD diffraction peak and NiSe in spectrogram2The standard spectra were completely identical, no significant impure phase was found, and the carbon peaks indicated by asterisks were significantly reduced in intensity relative to example 1 due to differences in carbon content.
Example 3
Using NiSe2The method for preparing the hydrogen production catalyst electrode by using the nanoparticle @ carbon nanosheet composite material comprises the following steps:
1): 40mg of NiSe2Dispersing the nanoparticle @ carbon nanosheet composite material into 1mL of ethanol, performing ultrasonic dispersion, adding 50 mu L of 5wt% Nafion solution, and performing ultrasonic dispersion to form a relatively stable suspension.
2): dripping the suspension liquid obtained in the step 1) onto a rotating disc electrode, drying at 50 ℃ to form an electrode, and performing performance test by using a three-electrode system.
Prepared by the above methodThe hydrogen evolution polarization curve of the sample is shown in FIG. 4, which is 10mA/cm in a solution with pH of 0.32The overpotential is only 0.18V at the current density of (2).
The above-described embodiments are disclosed as illustrative examples, and various changes and modifications can be made by those skilled in the art without departing from the scope of the present invention. The technical scope of the present invention is not limited to the embodiments described in the specification, and the above is only the preferred embodiments of the present invention, and is not intended to limit the present invention.
Claims (10)
1. NiSe2The preparation method of the nanoparticle @ carbon nanosheet composite material is characterized by comprising the following steps of: which comprises the following steps:
1) dissolving a divalent nickel salt, citric acid and urea into water together, evaporating the obtained solution to form gel, and carbonizing/reducing the gel at high temperature in a tubular furnace to form a Ni/C composite material;
2) the Ni/C composite material and selenium powder are subjected to gas phase diffusion combination reaction in a tubular furnace to obtain NiSe at a specific temperature2Nanoparticle @ carbon nanosheet composites.
2. The NiSe of claim 12The preparation method of the nanoparticle @ carbon nanosheet composite material is characterized by comprising the following steps of: in the step 1), the divalent nickel salt is nickel nitrate or ferric chloride.
3. The NiSe of claim 12The preparation method of the nanoparticle @ carbon nanosheet composite material is characterized by comprising the following steps of: in the step 1), the mass ratio of the divalent nickel salt to the citric acid to the urea is 0.2:1:5 to 1:1: 5.
4. The NiSe of claim 12The preparation method of the nanoparticle @ carbon nanosheet composite material is characterized by comprising the following steps of: in the step 1), the evaporation is carried out for 4 to 5 hours at the temperature of 80 to 85 ℃.
5. According to claimNiSe of claim 12The preparation method of the nanoparticle @ carbon nanosheet composite material is characterized by comprising the following steps of: in the step 1), the carbonization temperature is 500-800 ℃.
6. The NiSe of claim 12The preparation method of the nanoparticle @ carbon nanosheet composite material is characterized by comprising the following steps of: in the step 2), the mass ratio of the Ni/C composite material to the selenium powder is 1:5 to 1: 20.
7. The NiSe of claim 12The preparation method of the nanoparticle @ carbon nanosheet composite material is characterized by comprising the following steps of: in the step 2), the Ni/C composite material and the selenium powder are placed in a tube furnace, the temperature in the tube furnace is raised to 400-600 ℃ at the heating rate of 5 ℃/min, and then the heat treatment is carried out for 2-4h at the temperature of 400-600 ℃ to obtain the NiSe2Nanoparticle @ carbon nanosheet composites.
8. NiSe obtained by the preparation method according to any one of claims 1 to 72Nanoparticle @ carbon nanosheet composites.
9. The NiSe of claim 82The application of the nanoparticle @ carbon nanosheet composite material is characterized in that: the composite material is used for manufacturing hydrogen production catalyst electrodes.
10. The NiSe of claim 92The application of the nanoparticle @ carbon nanosheet composite material is characterized in that: the method for manufacturing the hydrogen production catalyst electrode comprises the following steps:
1) mixing NiSe2Dispersing the nanoparticle @ carbon nanosheet composite material into ethanol, adding a 5wt% Nafion solution, and performing ultrasonic dispersion to form a suspension;
2) and dripping the suspension liquid on a rotating disk electrode, and drying to form the electrode.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113410460A (en) * | 2021-06-11 | 2021-09-17 | 天津大学 | Three-dimensional ordered macroporous carbon-coated nickel selenide nanocrystalline material, preparation and application |
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| CN105947995A (en) * | 2016-04-22 | 2016-09-21 | 国家纳米科学中心 | NiSe2 nanosheet with selenium enriched on surface, preparation method thereof, and application thereof |
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