CN111111725A - Graphite-like carbon nitride supported nickel-cobalt-sulfur particle composite material, preparation method and application thereof - Google Patents
Graphite-like carbon nitride supported nickel-cobalt-sulfur particle composite material, preparation method and application thereof Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 128
- KAEHZLZKAKBMJB-UHFFFAOYSA-N cobalt;sulfanylidenenickel Chemical compound [Ni].[Co]=S KAEHZLZKAKBMJB-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 239000002245 particle Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000725 suspension Substances 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 27
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 24
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims abstract description 19
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims abstract description 10
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims abstract description 10
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- 239000000203 mixture Substances 0.000 claims description 49
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- 238000001354 calcination Methods 0.000 claims description 34
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
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- 238000004321 preservation Methods 0.000 claims description 18
- 239000002135 nanosheet Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 230000005588 protonation Effects 0.000 claims description 8
- 239000011858 nanopowder Substances 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- OFDYMSKSGFSLLM-UHFFFAOYSA-N Dinitramine Chemical compound CCN(CC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C(N)=C1[N+]([O-])=O OFDYMSKSGFSLLM-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims 2
- 238000001816 cooling Methods 0.000 abstract description 28
- 238000005406 washing Methods 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 10
- 238000004108 freeze drying Methods 0.000 abstract description 10
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- VRRFSFYSLSPWQY-UHFFFAOYSA-N sulfanylidenecobalt Chemical compound [Co]=S VRRFSFYSLSPWQY-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 abstract 1
- 238000010335 hydrothermal treatment Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- -1 Transition metal sulfide Chemical class 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 10
- 238000005119 centrifugation Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 238000012546 transfer Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000000634 powder X-ray diffraction Methods 0.000 description 8
- 238000011068 loading method Methods 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
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- 238000012827 research and development Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
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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
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- 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
-
- 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 graphite-like carbon nitride supported nickel-cobalt-sulfur particle composite material, a preparation method and application thereof, wherein graphite-like carbon nitride is prepared and uniformly dispersed in a mixed solution of water and ethanol; adding cobalt acetate tetrahydrate and nickel acetate tetrahydrate into the suspension, and mechanically stirring uniformly; adding ethylenediamine into the suspension and stirring uniformly; adding ammonia water into the suspension and stirring at room temperature; adding thiourea into the suspension, and preserving heat in a water bath kettle; placing the reaction kettle in an oven, and carrying out hydrothermal treatment on the reaction kettle; and (3) washing the sample for three times after cooling, centrifuging to collect a product, then freeze-drying, and placing the reaction kettle in an oven for hydrothermal reaction to obtain the graphite-like carbon nitride supported nickel-cobalt-sulfur composite material. The preparation method is simple in preparation process, convenient to operate and high in repeatability; the particle size of the cobalt-sulfur compound loaded by the graphite-like carbon nitride in situ is 10-50nm, and the distribution is uniform, so that the catalyst has an excellent energy catalysis application prospect.
Description
Technical Field
The invention relates to the technical field of efficient and cheap water electrolysis nano composite materials, in particular to a graphite-like carbon nitride supported nickel-cobalt-sulfur composite material and a preparation method and application thereof.
Background
With the rapid development of human society and global economy, the consumption of non-renewable resources such as coal, petroleum, natural gas and the like, the greenhouse effect is continuously intensified, and the environmental problem is increasingly prominent. Under the new condition of the era, the environmental and resource problems put forward new requirements on energy development, and the development of clean, pollution-free, safe and renewable novel energy is urgent, and becomes the focus of attention and research focus of human beings gradually. Among them, research and development of a high-performance hydrogen production system by water electrolysis becomes an important subject of current scientific research.
In electrolytic water, Hydrogen Evolution (HER) and Oxygen Evolution (OER) reactions play a very important role for energy conversion. However, the slow intrinsic kinetic rate of such reactions is largely a direct consequence of the low energy conversion efficiency of electrolyzed water. In particular, the slow kinetics of hydrogen evolution and oxygen evolution reactions are caused by the fact that the reactions involve diffusion adsorption of molecules, the formation of product molecules and the transmission and transfer of multiple protons and electrons, and a large overpotential is required to overcome the energy barrier of the reactions to ensure the reactions. Research and development of high-performance electrolytic water catalytic materials are important ways for reducing electrode polarization and improving reaction kinetic characteristics. Noble metal platinum (Pt) and its alloys are the best HER catalysts found so far, but their OER performance is poor; iridium (Ir) and ruthenium (Ru) based catalysts have the best catalytic performance for OER reactions, but have a poor catalytic effect for HER. As a noble metal-based electrode material, the expensive price greatly influences the large-scale application of the noble metal-based electrode material in the field of electrochemical technology. Therefore, the research and development of the non-noble metal electrolytic water catalytic material with rich reserves, low price, high catalytic activity and good stability has extremely important scientific significance and practical value.
Transition metal sulfide is an important electrochemical oxygen reduction catalyst, has the advantages of rich resources, low price, environmental friendliness and the like, has better activity and stability in an alkaline medium, and integrates the advantages of several aspects, so that the catalyst becomes one of important branches. First, the conventional view points that the metal active site is the main active center in the transition metal compound, and the electronic state and the surface active site of the metal atom can be further regulated and controlled by doping or substituting the metal element, so that the catalytic reaction kinetics of the catalyst can be effectively improved. Secondly, the material is subjected to micro-nano treatment to form a nano-level structure, so that the electrochemical active area of the electrode material is increased to a certain extent, and the reaction rate is promoted. Thirdly, the electronic structure of the surface of the catalyst is changed by compounding with other materials.
Disclosure of Invention
The invention overcomes the defects in the prior art, the reaction effect of noble metal platinum (Pt) based catalyst and iridium (Ir) and ruthenium (Ru) based catalyst on Hydrogen Evolution (HER) and Oxygen Evolution (OER) is not very good, and the expensive price of noble metal based electrode material can greatly influence the large-scale application of the noble metal based electrode material in the electrochemical technical field, and provides a graphite-shaped carbon nitride supported nickel-cobalt-sulfur composite material and a preparation method and application thereof; the particle size of the cobalt-sulfur compound loaded by the graphite-like carbon nitride in situ is 10-50nm, and the distribution is uniform, so that the catalyst has an excellent energy catalysis application prospect.
The purpose of the invention is realized by the following technical scheme.
The graphite carbon nitride loaded nickel-cobalt-sulfur composite material has nickel-cobalt-sulfur homogeneously distributed on graphite carbon nitride and pure NiCo2S4Composition of phase, NiCo2S4The particle size is 10-50nm, and the preparation method comprises the following steps:
step 1, sequentially calcining dinitramine twice to obtain graphite-like carbon nitride nanosheet powder, wherein the graphite-like carbon nitride nanosheet powder is heated from room temperature, is subjected to heat preservation and calcination, and is then naturally cooled to the room temperature, the heating rates are respectively 2-3 ℃/min and 4-6 ℃/min, the calcination temperatures are respectively 500-600 ℃ and 450-550 ℃, and the heat preservation time is 2-6 hours;
in step 1, the first calcination of dinitrile amine to obtain carbon nitride, and the second calcination of carbon nitride to obtain graphite-like carbon nitride, wherein the mass ratio of the first calcination of dinitrile amine to the first calcination of carbon nitride is (3000-5000): (500-800) (the dosage of the two is 3-5g and 800mg respectively in 500-5-.
In step 1, the room temperature is 20-25 ℃.
in the step 2, the amount of the graphite-like carbon nitride nanosheet powder obtained in the step 1 is 200 to 400 parts by mass, and each part by mass is 1 mg; the hydrochloric acid is aqueous hydrogen chloride solution, the concentration is 8-12M, and the amount of the hydrochloric acid is excessive relative to the graphite-shaped carbon nitride nanosheet powder.
In step 2, the protonated graphitic carbon nitride nanopowder is obtained after the protonated graphitic carbon nitride is centrifuged, cleaned and dried.
In the step 2, stirring is used for protonation, the stirring speed is 400-.
And 3, placing the suspension in which the graphite-like carbon nitride powder protonated in the step 2 is uniformly dispersed in a reaction container, adding cobalt acetate tetrahydrate, nickel acetate tetrahydrate, ammonia water and thiourea, stirring to uniformly disperse, carrying out water bath heat preservation treatment at 60-90 ℃ for 15-30 hours, and then carrying out hydrothermal heat preservation treatment at 150-200 ℃ for 3-8 hours to obtain the graphite-like carbon nitride supported nickel-cobalt-sulfur composite material, wherein the molar ratio of the cobalt acetate tetrahydrate, the nickel acetate tetrahydrate and the thiourea is (0.3-0.6): (0.15-0.3): (0.6-1.5) (i.e. the three are respectively 0.3-0.6 mmol, 0.15-0.3 mmol, 0.6-1.5 mmol), the ammonia water is used in 1-5 volume portions, the concentration is 1-10M, and each volume portion is 1 ml.
In the step 3, deionized water and ethanol are selected as solvents of the suspension, and the volume ratio of the deionized water to the ethanol is (1-5): (35-39), using 75-100 parts by mass of protonated graphitic carbon nitride powder, each part by mass being 1mg, placing the protonated graphitic carbon nitride nanopowder in a mixed solution of deionized water and ethanol, stirring to obtain a uniformly dispersed suspension of graphitic carbon nitride, wherein the stirring speed is 400-600r/min, the stirring time is 30-60 min, and the temperature is 20-25 ℃.
In step 3, the molar ratio of cobalt acetate tetrahydrate, nickel acetate tetrahydrate and thiourea is 2: 1: 4.
in the step 3, stirring is used to realize uniform dispersion, the stirring speed is 400-600r/min, and the stirring time is 10-30 min.
In step 3, ammonia is used in an amount of 1 to 5 parts by volume, at a concentration of 1 to 5M, each part by volume being 1 ml.
In step 3, after the hydrothermal reaction, centrifuging, washing, freezing and drying the reaction product to obtain the graphite-like carbon nitride supported nickel-cobalt-sulfur composite material, wherein the nickel-cobalt-sulfur in the graphite-like carbon nitride supported nickel-cobalt-sulfur composite material is prepared from a cobalt-sulfur compound (NiCo)2S4) Phase composition, nickel cobalt sulfur compound (NiCo) loaded in situ by graphite-like carbon nitride2S4) The particle size is 10-50nm, and the particles are uniformly distributed on the graphite-like carbon nitride.
In step 3, the water bath heat preservation treatment is carried out for 20-30 hours at 70-85 ℃, and then the hydrothermal heat preservation treatment is carried out for 5-8 hours at 160-200 ℃.
The invention has the beneficial effects that: the nickel-cobalt-sulfur nano particles provided by the invention are uniformly distributed on the graphite-like carbon nitride, the size is 10-50nm, and the unique microstructure is beneficial to the exposure of active sites and the infiltration of electrolyte, so that the improvement of electrochemical performance is promoted; the preparation method provided by the invention has the advantages of simple required equipment, convenient operation, controllable conditions, high repeatability and suitability for macro preparation; the nickel cobalt sulfur nanoparticles interact with the graphite-like carbon nitride through in-situ growth to improve the electronic structure of the surface. Thanks to the advantages, the electrode shows excellent electrolytic water catalytic activity and stability in alkaline solution, and has wide application prospect in fuel cells, catalytic electrolytic water and the like.
Drawings
FIG. 1 is an XRD (X-ray diffraction) curve diagram of a graphite-like carbon nitride supported nickel-cobalt-sulfur composite material prepared by the invention.
FIG. 2 is a transmission electron micrograph of the graphite-like carbon nitride supported nickel-cobalt-sulfur composite material prepared by the invention.
FIG. 3 is a graph showing the oxygen evolution performance of the graphite-like carbon nitride supported nickel-cobalt-sulfur composite material prepared by the present invention.
FIG. 4 is a graph showing the hydrogen evolution performance of the graphite-like carbon nitride supported nickel-cobalt-sulfur composite material prepared by the present invention.
FIG. 5 is a graph showing the stability of oxygen precipitation of the graphite-like carbon nitride supported nickel-cobalt-sulfur composite material prepared by the present invention.
FIG. 6 is a graph showing the hydrogen evolution stability of the graphite-like carbon nitride supported nickel-cobalt-sulfur composite material prepared by the present invention.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
Firstly, weighing 5g of dicyandiamide, loading the mixture into a crucible, calcining the mixture in a muffle furnace at 550 ℃, keeping the temperature for 4h at the heating rate of 2.3 ℃/min, and cooling the mixture along with the furnace to obtain the carbon nitride. And weighing 500mg of carbon nitride, calcining at 500 ℃ in a muffle furnace at the heating rate of 5 ℃/min, preserving heat for 4h, and cooling along with the furnace to obtain the graphite-like carbon nitride. 200mg of graphitic carbon nitride is weighed, added with 100ml of concentrated hydrochloric acid (10M) and stirred at the rotating speed of 600rpm for 120min at room temperature, centrifuged, cleaned and dried. Weighing 80mg of protonated graphite-like carbon nitride, pouring the protonated graphite-like carbon nitride into a polytetrafluoroethylene reaction kettle lining filled with 38ml of ethanol and 2ml of deionized water, and stirring at the rotating speed of 600rpm for 30min to obtain uniform suspension; 0.3mmol of cobalt acetate tetrahydrate (Co (CH) was weighed3COO)2·4H2O) and 0.15mmol (Ni (CH)3COO)2·4H2O) pouring the mixture into the prepared suspension, and mechanically stirring the mixture for 20min at the room temperature at the rotating speed of 600 rpm; 2ml of ammonia (5M) are added to the suspension by suction with a pipette and the mixture is allowed to continue at room temperatureMechanically stirring for 15min at the rotating speed of 600 rpm; weighing 0.9mmol of thiourea, adding the thiourea into the suspension, continuously mechanically stirring at the room temperature at the rotating speed of 600rpm for 20min, placing the reaction kettle in a water bath kettle, and preserving the heat at 80 ℃ for 20 h; the reaction kettle was placed in an oven and incubated at 170 ℃ for 3 h. After natural cooling, washing with water for three times, collecting the sample by centrifugation, and finally freeze-drying.
The XRD pattern of the graphite-like carbon nitride supported nickel cobalt sulfur particle composite material prepared by the above example is shown in figure 1, which shows that the composite material is made of NiCoS with higher purity4Composition, corresponding to JCPDS standard cards 73-1704.
The scanning electron micrograph is shown in fig. 2, which shows that the supported nickel-cobalt-sulfur particles are uniformly distributed on the graphite-like carbon nitride.
As shown in FIG. 3, the transmission electron microscope showed that the average particle size of nickel cobalt sulfide was 10-30nm and the nickel cobalt sulfide was uniformly supported on the graphite-like carbon nitride. The structure is convenient for exposing active sites and contacting and infiltrating electrolyte, and is beneficial to improving the electrochemical performance.
Preparing the prepared graphite-like carbon nitride loaded nickel-cobalt-sulfur particle composite material, isopropanol and a binder (Nafion) into electrode slurry in proportion, wherein the amounts of active substances, activated carbon, isopropanol and the binder are respectively 3mg, 7mg, 965 muL and 35 muL, coating 150 muL of the prepared electrode slurry on 1 x 1cm of carbon paper, using the electrode slurry as a working electrode to form a three-electrode system in an alkaline system for testing the electrochemical hydrogen separation/oxygen separation performance, and using a saturated calomel electrode as a reference electrode, a carbon rod as a counter electrode and 1.0mol/L of KOH solution as electrolyte to form the three-electrode system.
The electrochemical performance of the graphite-like carbon nitride supported nickel-cobalt-sulfur particle composite material is researched:
FIGS. 3 and 4 are graphs of the oxygen evolution and hydrogen evolution performance of the graphitic carbon nitride supported nickel cobalt sulfur particle composite material prepared in the above example in 1.0mol/L KOH saturated with nitrogen, respectively. It can be seen that: the oxygen evolution and hydrogen evolution activities of the nickel-cobalt-sulfur particle composite material loaded on the graphite-like carbon nitride are more excellent than those of pure nickel-cobalt-sulfur particles.
From FIGS. 5 and 6, oxygen evolution and hydrogen evolutionThe stability examination of the precipitation shows that after the continuous polarization for 12 hours, the solution is kept at 10mA cm-2The overpotential required by the current is increased by only 25mV and 20mV, which shows that the graphite-like carbon nitride loaded nickel-cobalt-sulfur particle composite material prepared by the method has excellent oxygen precipitation and hydrogen precipitation activity and stability as an electrolytic water catalytic material, and has good application prospects in fuel cells, metal-air batteries and electrolytic water.
Example 2
Firstly, weighing 5g of dicyandiamide, loading the mixture into a crucible, calcining the mixture in a muffle furnace at 550 ℃, keeping the temperature for 4h at the heating rate of 2.3 ℃/min, and cooling the mixture along with the furnace to obtain the carbon nitride. And weighing 500mg of carbon nitride, calcining at 500 ℃ in a muffle furnace at the heating rate of 5 ℃/min, preserving heat for 4h, and cooling along with the furnace to obtain the graphite-like carbon nitride. 200mg of graphite-like carbon nitride is weighed, added with 100ml of concentrated hydrochloric acid (10M) at the rotation speed of 400rpm, stirred at room temperature for 120min, centrifuged, cleaned and dried. Weighing 75mg of protonated graphite-like carbon nitride, pouring the protonated graphite-like carbon nitride into a polytetrafluoroethylene reaction kettle lining filled with 38ml of ethanol and 2ml of deionized water, and stirring at the rotating speed of 600rpm for 30min to obtain uniform suspension; 0.3mmol of cobalt acetate tetrahydrate (Co (CH) was weighed3COO)2·4H2O) and 0.15mmol (Ni (CH)3COO)2·4H2O) pouring the mixture into the prepared suspension, and mechanically stirring the mixture for 20min at the room temperature at the rotating speed of 600 rpm; absorbing 2ml of ammonia water by using a liquid transfer gun, adding the ammonia water into the suspension, and continuously mechanically stirring the mixture at the room temperature at the rotating speed of 600rpm for 15 min; weighing 0.9mmol of thiourea, adding the thiourea into the suspension, continuously mechanically stirring at the room temperature at the rotating speed of 600rpm for 20min, placing the reaction kettle in a water bath kettle, and preserving the heat at 80 ℃ for 20 h; the reaction kettle is placed in an oven and kept at 170 ℃ for 6 h. After natural cooling, washing with water for three times, collecting the sample by centrifugation, and finally freeze-drying.
The graphite-like carbon nitride loaded nickel-cobalt-sulfur particle composite material can be obtained by utilizing X-ray powder diffraction and scanning and a transmission electron microscope to characterize the structure and the morphology of the composite material. The average grain diameter of the nickel-cobalt-sulfur is 20-40nm, and the nickel-cobalt-sulfur is uniformly loaded on the graphite-like carbon nitride.
Example 3
Firstly, 5g of dicyandiamide is weighed and put into a crucible,calcining at 550 ℃ in a muffle furnace, keeping the temperature for 4h at the heating rate of 2.3 ℃/min, and cooling along with the furnace to obtain the carbon nitride. And weighing 500mg of carbon nitride, calcining at 500 ℃ in a muffle furnace at the heating rate of 5 ℃/min, preserving heat for 4h, and cooling along with the furnace to obtain the graphite-like carbon nitride. 200mg of graphitic carbon nitride is weighed, added with 100ml of concentrated hydrochloric acid (10M) and stirred at the rotating speed of 450rpm for 120min at room temperature, centrifuged, cleaned and dried. Weighing 100mg of protonated graphite-like carbon nitride, pouring the protonated graphite-like carbon nitride into a polytetrafluoroethylene reaction kettle lining filled with 38ml of ethanol and 2ml of deionized water, and stirring at the rotating speed of 600rpm for 30min to obtain uniform suspension; 0.3mmol of cobalt acetate tetrahydrate (Co (CH) was weighed3COO)2·4H2O) and 0.15mmol (Ni (CH)3COO)2·4H2O) pouring the mixture into the prepared suspension, and mechanically stirring the mixture for 20min at the room temperature at the rotating speed of 600 rpm; absorbing 2ml of ammonia water by using a liquid transfer gun, adding the ammonia water into the suspension, and continuously mechanically stirring the mixture at the room temperature at the rotating speed of 600rpm for 15 min; weighing 0.9mmol of thiourea, adding the thiourea into the suspension, continuously mechanically stirring at the room temperature at the rotating speed of 600rpm for 20min, placing the reaction kettle in a water bath kettle, and preserving the heat at 80 ℃ for 20 h; the reaction kettle is placed in an oven and is kept at 170 ℃ for 8 h. After natural cooling, washing with water for three times, collecting the sample by centrifugation, and finally freeze-drying.
The graphite-like carbon nitride loaded nickel-cobalt-sulfur particle composite material can be obtained by utilizing X-ray powder diffraction and scanning and a transmission electron microscope to characterize the structure and the morphology of the composite material. The average grain diameter of the nickel cobalt sulfur is 30-50nm, and the nickel cobalt sulfur is uniformly loaded on the graphite-like carbon nitride.
Example 4
Firstly, weighing 5g of dicyandiamide, loading the mixture into a crucible, calcining the mixture in a muffle furnace at 550 ℃, keeping the temperature for 4h at the heating rate of 2.3 ℃/min, and cooling the mixture along with the furnace to obtain the carbon nitride. And weighing 500mg of carbon nitride, calcining at 500 ℃ in a muffle furnace at the heating rate of 5 ℃/min, preserving heat for 4h, and cooling along with the furnace to obtain the graphite-like carbon nitride. 200mg of graphite-like carbon nitride is weighed, added with 100ml of concentrated hydrochloric acid (10M) at the rotation speed of 550rpm, stirred at room temperature for 120min, centrifuged, cleaned and dried. Weighing 90mg of protonated graphite-like carbon nitride, pouring the protonated graphite-like carbon nitride into a polytetrafluoroethylene reaction kettle lining filled with 38ml of ethanol and 2ml of deionized water, and stirring the mixture at the rotating speed of 600rpm for 30min to enable the mixture to become uniform suspensionLiquid; 0.3mmol of cobalt acetate tetrahydrate (Co (CH) was weighed3COO)2·4H2O) and 0.15mmol (Ni (CH)3COO)2·4H2O) pouring the mixture into the prepared suspension, and mechanically stirring the mixture for 20min at the room temperature at the rotating speed of 600 rpm; absorbing 2ml of ammonia water by using a liquid transfer gun, adding the ammonia water into the suspension, and continuously mechanically stirring the mixture at the room temperature at the rotating speed of 600rpm for 15 min; weighing 0.9mmol of thiourea, adding the thiourea into the suspension, continuously mechanically stirring at the room temperature at the rotating speed of 600rpm for 20min, placing the reaction kettle in a water bath kettle, and preserving heat at 80 ℃ for 25 h; the reaction kettle was placed in an oven and incubated at 170 ℃ for 3 h. After natural cooling, washing with water for three times, collecting the sample by centrifugation, and finally freeze-drying.
The graphite-like carbon nitride loaded nickel-cobalt-sulfur particle composite material can be obtained by utilizing X-ray powder diffraction and scanning and a transmission electron microscope to characterize the structure and the morphology of the composite material. The average grain diameter of the nickel cobalt sulfur is 20-30nm, and the nickel cobalt sulfur is uniformly loaded on the graphite-like carbon nitride.
Example 5
Firstly, weighing 5g of dicyandiamide, loading the mixture into a crucible, calcining the mixture in a muffle furnace at 550 ℃, keeping the temperature for 4h at the heating rate of 2.3 ℃/min, and cooling the mixture along with the furnace to obtain the carbon nitride. And weighing 500mg of carbon nitride, calcining at 500 ℃ in a muffle furnace at the heating rate of 5 ℃/min, preserving heat for 4h, and cooling along with the furnace to obtain the graphite-like carbon nitride. 200mg of graphite-like carbon nitride is weighed, added with 100ml of concentrated hydrochloric acid (10M) at the rotation speed of 500rpm, stirred at room temperature for 120min, centrifuged, cleaned and dried. Weighing 85mg of protonated graphite-like carbon nitride, pouring the protonated graphite-like carbon nitride into a polytetrafluoroethylene reaction kettle lining filled with 38ml of ethanol and 2ml of deionized water, and stirring at the rotating speed of 600rpm for 30min to obtain uniform suspension; 0.3mmol of cobalt acetate tetrahydrate (Co (CH) was weighed3COO)2·4H2O) and 0.15mmol (Ni (CH)3COO)2·4H2O) pouring the mixture into the prepared suspension, and mechanically stirring the mixture for 20min at the room temperature at the rotating speed of 600 rpm; absorbing 2ml of ammonia water by using a liquid transfer gun, adding the ammonia water into the suspension, and continuously mechanically stirring the mixture at the room temperature at the rotating speed of 600rpm for 15 min; weighing 0.8mmol of thiourea, adding the thiourea into the suspension, continuously mechanically stirring at the room temperature at the rotating speed of 600rpm for 20min, placing the reaction kettle in a water bath kettle, and preserving the heat at 80 ℃ for 30 h; will be provided withThe reaction kettle is placed in an oven and is kept at 170 ℃ for 6 h. After natural cooling, washing with water for three times, collecting the sample by centrifugation, and finally freeze-drying.
The graphite-like carbon nitride loaded nickel-cobalt-sulfur particle composite material can be obtained by utilizing X-ray powder diffraction and scanning and a transmission electron microscope to characterize the structure and the morphology of the composite material. The average grain diameter of the nickel cobalt sulfur is 40-50nm, and the nickel cobalt sulfur is uniformly loaded on the graphite-like carbon nitride.
Example 6
Firstly, weighing 5g of dicyandiamide, loading the dicyandiamide into a crucible, calcining the dicyandiamide in a muffle furnace at 500 ℃, keeping the temperature for 6 hours at the heating rate of 2 ℃/min, and cooling the furnace to obtain the carbon nitride. Weighing 800mg of carbon nitride, calcining at 450 ℃ in a muffle furnace at the heating rate of 4 ℃/min, preserving heat for 6h, and cooling along with the furnace to obtain the graphite-like carbon nitride. 400mg of graphitic carbon nitride is weighed, added with 100ml of concentrated hydrochloric acid (9M) at the rotating speed of 600rpm, stirred for 160min at room temperature, centrifuged, cleaned and dried. Weighing 100mg of protonated graphite-like carbon nitride, pouring the protonated graphite-like carbon nitride into a polytetrafluoroethylene reaction kettle lining filled with 39ml of ethanol and 1ml of deionized water, and stirring at the rotating speed of 600rpm for 25min to obtain uniform suspension; 0.3mmol of cobalt acetate tetrahydrate (Co (CH) was weighed3COO)2·4H2O) and 0.1mmol (Ni (CH)3COO)2·4H2O) pouring the mixture into the prepared suspension, and mechanically stirring the mixture at the rotating speed of 600rpm for 25min at room temperature; absorbing 5ml of ammonia water by using a liquid transfer gun, adding the ammonia water into the suspension, and continuously mechanically stirring the mixture at the room temperature at the rotating speed of 600rpm for 20 min; weighing 1.2mmol of thiourea, adding the thiourea into the suspension, continuously mechanically stirring at the room temperature at the rotating speed of 600rpm for 35min, placing the reaction kettle in a water bath kettle, and keeping the temperature at 85 ℃ for 15 h; the reaction kettle is placed in an oven and is kept at 200 ℃ for 3 h. After natural cooling, washing with water for three times, collecting the sample by centrifugation, and finally freeze-drying.
The graphite-like carbon nitride loaded nickel-cobalt-sulfur particle composite material can be obtained by utilizing X-ray powder diffraction and scanning and a transmission electron microscope to characterize the structure and the morphology of the composite material. The average grain diameter of the nickel-cobalt-sulfur is 10-20nm, and the nickel-cobalt-sulfur is uniformly loaded on the graphite-like carbon nitride.
Example 7
First, 3g of dicyandiamide was weighed inCalcining at 600 ℃ in a muffle furnace in a crucible, keeping the temperature for 2h at the heating rate of 3 ℃/min, and cooling with the furnace to obtain the carbon nitride. And weighing 500mg of carbon nitride, calcining at 550 ℃ in a muffle furnace at the heating rate of 6 ℃/min, preserving heat for 2h, and cooling along with the furnace to obtain the graphite-like carbon nitride. 200mg of graphitic carbon nitride is weighed, added with 100ml of concentrated hydrochloric acid (12M) at the rotating speed of 400pm, stirred for 100min at room temperature, centrifuged, cleaned and dried. Weighing 75mg of protonated graphite-like carbon nitride, pouring the protonated graphite-like carbon nitride into a polytetrafluoroethylene reaction kettle lining filled with 37ml of ethanol and 3ml of deionized water, and stirring at the rotating speed of 400rpm for 20min to obtain uniform suspension; 0.3mmol of cobalt acetate tetrahydrate (Co (CH) was weighed3COO)2·4H2O) and 0.3mmol (Ni (CH)3COO)2·4H2O) pouring the mixture into the prepared suspension, and mechanically stirring the mixture for 8min at the rotating speed of 400rpm at room temperature; sucking 1ml of ammonia water by using a liquid transfer gun, adding the ammonia water into the suspension, and continuously mechanically stirring at the room temperature at the rotating speed of 600rpm for 10 min; weighing 0.8mmol of thiourea, adding the thiourea into the suspension, continuously mechanically stirring at the room temperature at the rotating speed of 400rpm for 10min, placing the reaction kettle in a water bath kettle, and preserving heat at 65 ℃ for 30 h; the reaction kettle is placed in an oven and is kept at 150 ℃ for 8 h. After natural cooling, washing with water for three times, collecting the sample by centrifugation, and finally freeze-drying.
The graphite-like carbon nitride loaded nickel-cobalt-sulfur particle composite material can be obtained by utilizing X-ray powder diffraction and scanning and a transmission electron microscope to characterize the structure and the morphology of the composite material. The average grain diameter of the nickel cobalt sulfur is 40-50nm, and the nickel cobalt sulfur is uniformly loaded on the graphite-like carbon nitride.
Example 8
Firstly, weighing 4g of dicyandiamide, loading the mixture into a crucible, calcining the mixture in a muffle furnace at 540 ℃, keeping the temperature for 3h at the heating rate of 2.2 ℃/min, and cooling the mixture along with the furnace to obtain the carbon nitride. And weighing 400mg of carbon nitride, calcining at 490 ℃ in a muffle furnace at the heating rate of 4.8 ℃/min, preserving heat for 3h, and cooling along with the furnace to obtain the graphite-like carbon nitride. 300mg of graphitic carbon nitride is weighed, added with 100ml of concentrated hydrochloric acid (11M) at 650rpm and stirred for 120min at room temperature, centrifuged, cleaned and dried. Weighing 80mg of protonated graphite-like carbon nitride, pouring the protonated graphite-like carbon nitride into a polytetrafluoroethylene reaction kettle lining filled with 38ml of ethanol and 2ml of deionized water, and stirring at the rotating speed of 500rpm for 30min to ensure that the protonated graphite-like carbon nitride is uniformThe suspension of (4); 0.3mmol of cobalt acetate tetrahydrate (Co (CH) was weighed3COO)2·4H2O) and 0.15mmol (Ni (CH)3COO)2·4H2O) pouring the mixture into the prepared suspension, and mechanically stirring the mixture for 10min at room temperature at the rotating speed of 500 rpm; absorbing 3ml of ammonia water by using a liquid transfer gun, adding the ammonia water into the suspension, and continuously mechanically stirring the mixture at the room temperature at the rotating speed of 600rpm for 12 min; weighing 0.6mmol of thiourea, adding the thiourea into the suspension, continuously mechanically stirring at the room temperature at the rotating speed of 500rpm for 30min, placing the reaction kettle in a water bath kettle, and preserving heat at 80 ℃ for 25 h; the reaction kettle is placed in an oven and kept at 170 ℃ for 6 h. After natural cooling, washing with water for three times, collecting the sample by centrifugation, and finally freeze-drying.
The graphite-like carbon nitride loaded nickel-cobalt-sulfur particle composite material can be obtained by utilizing X-ray powder diffraction and scanning and a transmission electron microscope to characterize the structure and the morphology of the composite material. The average grain diameter of the nickel cobalt sulfur is 20-30nm, and the nickel cobalt sulfur is uniformly loaded on the graphite-like carbon nitride.
Example 9
Firstly, weighing 4g of dicyandiamide, loading the mixture into a crucible, calcining the mixture in a muffle furnace at 560 ℃, keeping the temperature for 5h at the heating rate of 2.4 ℃/min, and cooling the mixture along with the furnace to obtain the carbon nitride. 400mg of carbon nitride is weighed and calcined in a muffle furnace at 510 ℃, the heating rate is 5.2 ℃/min, the temperature is kept for 5h, and the graphite-like carbon nitride is obtained after furnace cooling. 300mg of graphitic carbon nitride is weighed, added with 100ml of concentrated hydrochloric acid (12M) at the rotating speed of 350rpm, stirred for 150min at room temperature, centrifuged, cleaned and dried. Weighing 90mg of protonated graphite-like carbon nitride, pouring the protonated graphite-like carbon nitride into a polytetrafluoroethylene reaction kettle lining filled with 39ml of ethanol and 1ml of deionized water, and stirring at the rotating speed of 550rpm for 40min to obtain uniform suspension; 0.3mmol of cobalt acetate tetrahydrate (Co (CH) was weighed3COO)2·4H2O) and 0.1mmol (Ni (CH)3COO)2·4H2O) pouring the mixture into the prepared suspension, and mechanically stirring the mixture for 15min at the room temperature at the rotating speed of 550 rpm; 3ml of ammonia water is sucked by a liquid transfer gun and added into the suspension, and mechanical stirring is carried out at the room temperature at the rotating speed of 600rpm for 18 min; weighing 1.5mmol of thiourea, adding into the suspension, continuously mechanically stirring at room temperature at 550rpm for 25min, placing the reaction kettle in a water bath, and keeping the temperature at 60 deg.C30 h; the reaction kettle is placed in an oven and is kept at 150 ℃ for 8 h. After natural cooling, washing with water for three times, collecting the sample by centrifugation, and finally freeze-drying.
The graphite-like carbon nitride loaded nickel-cobalt-sulfur particle composite material can be obtained by utilizing X-ray powder diffraction and scanning and a transmission electron microscope to characterize the structure and the morphology of the composite material. The average grain diameter of the nickel cobalt sulfur is 30-40nm, and the nickel cobalt sulfur is uniformly loaded on the graphite-like carbon nitride.
The preparation of the graphite-like carbon nitride loaded nickel-cobalt-sulfur particle composite material can be realized by adjusting the process parameters according to the content of the invention, and the performance basically consistent with the invention is shown. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. The graphite-like carbon nitride supported nickel-cobalt-sulfur composite material is characterized in that nickel-cobalt-sulfur is uniformly distributed on graphite-like carbon nitride, and the nickel-cobalt-sulfur is made of pure NiCo2S4Composition of phase, NiCo2S4The particle size is 10-50nm, and the method comprises the following steps:
step 1, sequentially calcining dinitramine twice to obtain graphite-like carbon nitride nanosheet powder, wherein the graphite-like carbon nitride nanosheet powder is heated from room temperature, is subjected to heat preservation and calcination, and is then naturally cooled to the room temperature, the heating rates are respectively 2-3 ℃/min and 4-6 ℃/min, the calcination temperatures are respectively 500-600 ℃ and 450-550 ℃, and the heat preservation time is 2-6 hours;
step 2, putting the graphite-shaped carbon nitride nanosheet powder obtained in the step 1 into hydrochloric acid for protonation to obtain protonized graphite-shaped carbon nitride nanopowder;
and 3, placing the suspension in which the graphite-like carbon nitride powder protonated in the step 2 is uniformly dispersed in a reaction container, adding cobalt acetate tetrahydrate, nickel acetate tetrahydrate, ammonia water and thiourea, stirring to uniformly disperse, carrying out water bath heat preservation treatment at 60-90 ℃ for 15-30 hours, and then carrying out hydrothermal heat preservation treatment at 150-200 ℃ for 3-8 hours to obtain the graphite-like carbon nitride supported nickel-cobalt-sulfur composite material, wherein the molar ratio of the cobalt acetate tetrahydrate, the nickel acetate tetrahydrate and the thiourea is (0.3-0.6): (0.15-0.3): (0.6-1.5), the dosage of ammonia water is 1-5 volume parts, and the concentration is 1-10M.
2. The graphitic carbon nitride-supported nickel cobalt sulfur composite according to claim 1, wherein in step 1, the first calcined dinitrile amine is calcined to obtain carbon nitride, and the carbon nitride obtained by the first calcination is calcined for a second time to obtain graphitic carbon nitride, wherein the mass ratio of the first calcined dinitrile amine to the carbon nitride obtained by the first calcination is (3000-5000): (500-800) (the dosage of the two is 3-5g and 800mg respectively in 500-5-; the room temperature is 20-25 ℃.
3. The graphitic carbon nitride supported nickel cobalt sulfur composite material according to claim 1, wherein in step 2, the amount of the graphitic carbon nitride nanosheet powder obtained in step 1 is 200 to 400 parts by mass, each part by mass being 1 mg; the hydrochloric acid is aqueous solution of hydrogen chloride, and the concentration is 8-12M; stirring is used for protonation, the stirring speed is 400-600r/min, the stirring time is 120-150min, and the protonation temperature is 20-25 ℃.
4. The graphitic carbon nitride supported nickel cobalt sulfur composite material according to claim 1, wherein in step 3, deionized water and ethanol are selected as solvents of the suspension, and the volume ratio of the deionized water to the ethanol is (1-5): (35-39), using 75-100 parts by mass of protonated graphitic carbon nitride powder, each part by mass being 1mg, placing the protonated graphitic carbon nitride nanopowder in a mixed solution of deionized water and ethanol, and stirring to obtain a uniformly dispersed suspension of graphitic carbon nitride; the stirring speed is 400-600r/min, the stirring time is 30-60 min, and the temperature is 20-25 ℃.
5. The graphitic carbon nitride-supported nickel cobalt sulfur composite according to claim 1, wherein in step 3, the molar ratio of cobalt acetate tetrahydrate, nickel acetate tetrahydrate, and thiourea is 2: 1: 4; the ammonia water is used in 1-5 volume portions and the concentration is 1-5M, stirring is used to realize uniform dispersion, the stirring speed is 400-600r/min, and the stirring time is 10-30 min; the water bath heat preservation treatment is carried out for 20 to 30 hours at the temperature of between 70 and 85 ℃, and then the hydrothermal heat preservation treatment is carried out for 5 to 8 hours at the temperature of between 160 and 200 ℃.
6. The preparation method of the graphite-like carbon nitride supported nickel-cobalt-sulfur composite material is characterized by comprising the following steps of:
step 1, sequentially calcining dinitramine twice to obtain graphite-like carbon nitride nanosheet powder, wherein the graphite-like carbon nitride nanosheet powder is heated from room temperature, is subjected to heat preservation and calcination, and is then naturally cooled to the room temperature, the heating rates are respectively 2-3 ℃/min and 4-6 ℃/min, the calcination temperatures are respectively 500-600 ℃ and 450-550 ℃, and the heat preservation time is 2-6 hours;
step 2, putting the graphite-shaped carbon nitride nanosheet powder obtained in the step 1 into hydrochloric acid for protonation to obtain protonized graphite-shaped carbon nitride nanopowder;
and 3, placing the suspension in which the graphite-like carbon nitride powder protonated in the step 2 is uniformly dispersed in a reaction container, adding cobalt acetate tetrahydrate, nickel acetate tetrahydrate, ammonia water and thiourea, stirring to uniformly disperse, carrying out water bath heat preservation treatment at 60-90 ℃ for 15-30 hours, and then carrying out hydrothermal heat preservation treatment at 150-200 ℃ for 3-8 hours to obtain the graphite-like carbon nitride supported nickel-cobalt-sulfur composite material, wherein the molar ratio of the cobalt acetate tetrahydrate, the nickel acetate tetrahydrate and the thiourea is (0.3-0.6): (0.15-0.3): (0.6-1.5), the dosage of ammonia water is 1-5 volume parts, and the concentration is 1-10M.
7. The method for preparing a graphitic carbon nitride-supported nickel cobalt sulfur composite material according to claim 6, wherein in step 1, the first calcined dinitrile amine is used to obtain carbon nitride, and the carbon nitride obtained by the first calcination is subjected to a second calcination to obtain graphitic carbon nitride, wherein the mass ratio of the first calcined dinitrile amine to the carbon nitride obtained by the first calcination is (3000-5000): (500-800) (the dosage of the two is 3-5g and 800mg respectively in 500-5-; the room temperature is 20-25 ℃.
8. The method for preparing a graphitic carbon nitride-supported nickel cobalt sulfur composite material according to claim 6, wherein in the step 2, the amount of the graphitic carbon nitride nanosheet powder obtained in the step 1 is 200 to 400 parts by mass, each part by mass being 1 mg; the hydrochloric acid is aqueous solution of hydrogen chloride, and the concentration is 8-12M; stirring is used for protonation, the stirring speed is 400-600r/min, the stirring time is 120-150min, and the protonation temperature is 20-25 ℃.
9. The preparation method of the graphitic carbon nitride supported nickel cobalt sulfur composite material according to claim 6, wherein in the step 3, deionized water and ethanol are selected as solvents of the suspension, and the volume ratio of the deionized water to the ethanol is (1-5): (35-39), using 75-100 parts by mass of protonated graphitic carbon nitride powder, each part by mass being 1mg, placing the protonated graphitic carbon nitride nanopowder in a mixed solution of deionized water and ethanol, and stirring to obtain a uniformly dispersed suspension of graphitic carbon nitride; the stirring speed is 400-600r/min, the stirring time is 30-60 min, and the temperature is 20-25 ℃; the molar ratio of cobalt acetate tetrahydrate, nickel acetate tetrahydrate and thiourea is 2: 1: 4; the ammonia water is used in 1-5 volume portions and the concentration is 1-5M, stirring is used to realize uniform dispersion, the stirring speed is 400-600r/min, and the stirring time is 10-30 min; the water bath heat preservation treatment is carried out for 20 to 30 hours at the temperature of between 70 and 85 ℃, and then the hydrothermal heat preservation treatment is carried out for 5 to 8 hours at the temperature of between 160 and 200 ℃.
10. Use of the graphitic carbon nitride-supported nickel cobalt sulphur composite according to any of claims 1 to 5 in fuel cells, metal air cells and catalytic electrolysis of water.
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