CN109453790A - A kind of nanosphere and preparation method thereof of the doped carbon encapsulation transient metal sulfide applied to electro-catalysis - Google Patents
A kind of nanosphere and preparation method thereof of the doped carbon encapsulation transient metal sulfide applied to electro-catalysis Download PDFInfo
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- CN109453790A CN109453790A CN201811080604.6A CN201811080604A CN109453790A CN 109453790 A CN109453790 A CN 109453790A CN 201811080604 A CN201811080604 A CN 201811080604A CN 109453790 A CN109453790 A CN 109453790A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 24
- 229910052976 metal sulfide Inorganic materials 0.000 title claims abstract description 20
- 239000002077 nanosphere Substances 0.000 title claims abstract description 20
- 230000001052 transient effect Effects 0.000 title claims abstract description 20
- 238000005538 encapsulation Methods 0.000 title claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 229960003638 dopamine Drugs 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 150000003233 pyrroles Chemical group 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 238000006722 reduction reaction Methods 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 239000003643 water by type Substances 0.000 description 15
- 238000013019 agitation Methods 0.000 description 11
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 10
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 9
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000005518 electrochemistry Effects 0.000 description 7
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920000128 polypyrrole Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000017105 transposition Effects 0.000 description 5
- 238000000840 electrochemical analysis Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- WTURHYSHERRQHM-UHFFFAOYSA-N [Ni].[Ni]=S Chemical compound [Ni].[Ni]=S WTURHYSHERRQHM-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- YGHCWPXPAHSSNA-UHFFFAOYSA-N nickel subsulfide Chemical group [Ni].[Ni]=S.[Ni]=S YGHCWPXPAHSSNA-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- B01J35/33—
-
- B01J35/51—
-
- 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 kind of nanosphere and preparation method thereof of doped carbon encapsulation transient metal sulfide applied to electro-catalysis, chemical formulas are as follows: M x S y @NOSC, M Fe, Co or Ni,x、yFor sulfide coefficient, value range is respectively as follows: 9≤x≤ 1,9≤y≤1.The nanosphere of doped carbon encapsulation transient metal sulfide of the present invention, under the premise of guaranteeing architectural characteristic, it finds and has obtained a kind of transition metal nanosphere that can be wrapped up by high temperature cabonization one-step synthesis doped carbon, it is applied to electro-catalysis water decomposition, under acidic, neutral and alkaline conditions, the overpotential that liberation of hydrogen and oxygen evolution reaction can be substantially reduced improves the selectivity of oxygen reduction reaction.The present invention emphasizes the micron ball of the carbon package transient metal sulfide of three doping (N, O, S), and synthetic method is simple unique and is applicable in the scale produced.
Description
Technical field
The present invention relates to a kind of nanosphere of doped carbon encapsulation transient metal sulfide applied to electro-catalysis and its preparations
Method.
Background technique
Continue and a series of problems largely is brought to the consumption of conventional fossil fuel, e.g., energy crisis and the whole world become
It warms up.Based on this, many scientists are dedicated to research and development cleaning sustainable energy and storage equipment, for example, Hydrogen Energy and fuel cell
Deng.Electro-catalysis water decomposition provides effective way for the generation of Hydrogen Energy, main electrochemical process include evolving hydrogen reaction (HER),
Oxygen evolution reaction (OER) and oxygen reduction reaction (ORR).But since its reaction carries out slowly, needing additionally to use catalyst, mesh
Preceding widely used noble metal-based catalysts are at high price, and existing reserves are few, and stability is poor, therefore, develop cheap and abundant
Catalyst is imperative
The present invention has developed a kind of N, O, S element codope carbon packet based on elements such as the carbon of earth rich reserves, sulphur, cobalt, nickel
Nickel sulfide micron ball is wrapped up in, and logical peracid treatment realizes the mutually conversion of surface sulfide nickel, so as to form three-decker.Through electrification
Learn test, it was demonstrated that the material has good HER, OER and ORR performance.
Summary of the invention
Electrocatalytic decomposition water overpotential can be reduced the purpose of the present invention is to provide a kind of, the doping suitable for full pH range
The nano-sphere catalyst of carbon encapsulation transient metal sulfide.
Another mesh of the invention is to provide the system of the nano-sphere catalyst of above-mentioned doped carbon encapsulation transient metal sulfide
Preparation Method.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of nanosphere of the doped carbon encapsulation transient metal sulfide applied to electro-catalysis, chemical formula are as follows: M x S y @NOSC, M
For Fe, Co or Ni,x、yFor sulfide coefficient, value range is respectively as follows: 9≤x≤ 1,9≤y≤1.
The preparation method of the nanosphere of the above-mentioned doped carbon encapsulation transient metal sulfide applied to electro-catalysis, including it is as follows
Step: weighing oxidant, is dissolved in deionized water, and high polymer monomer is added dropwise and is polymerize, transition metal is added after dry
Object is closed to be chelated, dry, grinding carries out multistep sintering, after be cooled to room temperature, product is ground and obtains product.
Preferably, the oxidant is ammonium persulfate or iron chloride in above-mentioned preparation method；The macromolecule
Monomer is pyrroles, aniline or dopamine；The transistion metal compound is its oxide, chloride, nitrate, carbonate, grass
The mixture of any one compound or multiple compounds composition in hydrochlorate.
Preferably, in above-mentioned preparation method, the sintering temperature is 600 ~ 1000 DEG C, sintering time is 10 ~
30 h。
Compared with prior art, the present invention has following the utility model has the advantages that doped carbon encapsulation transient metal sulfide of the present invention
Nanosphere, guarantee architectural characteristic under the premise of, searching obtained one kind can be by high temperature cabonization one-step synthesis doped carbon packet
The transition metal nanosphere wrapped up in, is applied to electro-catalysis water decomposition, under acidic, neutral and alkaline conditions, can be significantly
The overpotential for reducing liberation of hydrogen and oxygen evolution reaction, improves the selectivity of oxygen reduction reaction.The present invention emphasizes the carbon of three doping (N, O, S)
The micron ball of transient metal sulfide is wrapped up, synthetic method is simple unique and is applicable in the scale produced.
Detailed description of the invention
Fig. 1 is that the x-ray powder for the nanosphere that doped carbon prepared by embodiment 1/4/5 encapsulates transient metal sulfide spreads out
Penetrate map.
Fig. 2 is the X-ray powder diffraction figure for the nanosphere that doped carbon prepared by embodiment 2 encapsulates transient metal sulfide
Spectrum.
Fig. 3 is the HRTEM map for the nanosphere that doped carbon prepared by embodiment 1 encapsulates transient metal sulfide.
Fig. 4 is the HRTEM map for the nanosphere that doped carbon prepared by embodiment 2 encapsulates transient metal sulfide.
Fig. 5 is the HRTEM map for the nanosphere that doped carbon prepared by embodiment 3 encapsulates transient metal sulfide.
Fig. 6 is the Electrochemical oxygen evolution (OER) for the nanosphere that doped carbon prepared by embodiment 2 encapsulates transient metal sulfide
With electrochemistry liberation of hydrogen (HER) map.
Specific embodiment
Embodiment 1
Ammonium persulfate ((NH4) is weighed respectively2S2O8) 4.2 g are dissolved in 40 mL deionized waters, (0 ~ 5 DEG C) magnetic under conditions of ice bath
Power stirring, is slowly inwardly added dropwise 620 μ L pyrrole monomers, keeps condition of ice bath, continues 5 h of magnetic agitation.It is transferred to evaporating dish
In, dry 24 h at 80 DEG C.It takes out, grinding is scattered in 10 mL deionized waters, by nickel chloride (NiCl2·6H2O) 1.093
G is dissolved in 10 mL deionized waters, is added dropwise in above-mentioned polypyrrole dispersion liquid, 6 h of magnetic agitation.Transposition is in evaporating dish, in 80
After being dried overnight at DEG C, it is uniform to take out grinding.It is pyrolyzed in tube furnace.1) 300 are risen to from room temperature with the rate of 1 DEG C/min
DEG C, keep the temperature 3 h.2) 900 DEG C are risen to the rate of 10 DEG C/min, keeps the temperature 2 h.Cooled to room temperature obtains black powder.
The product X-ray powder diffraction result is as shown in Figure 1.As shown in figure 1 shown in XRD spectrum, all diffraction maximums can be with Ni3S2Standard
Peak (PDF#44-1418) is corresponding.Show that the sample has apparent core-shell structure by HRTEM Fig. 3, i.e. outer layer is doping
Carbon-coating, internal layer Ni3S2 Core.Pass through electro-chemical test, it was demonstrated that the material has good electrochemistry HER, OER and ORR performance.
Embodiment 2
Ammonium persulfate ((NH4) is weighed respectively2S2O8) 4.2 g are dissolved in 40 mL deionized waters, (0 ~ 5 DEG C) magnetic under conditions of ice bath
Power stirring, is slowly inwardly added dropwise 620 μ L pyrrole monomers, keeps condition of ice bath, continues 5 h of magnetic agitation.It is transferred to evaporating dish
In, dry 24 h at 80 DEG C.It takes out, grinding is scattered in 10 mL deionized waters, by cobalt chloride (CoCl2·6H2O) 1.094
G is dissolved in 10 mL deionized waters, is added dropwise in above-mentioned polypyrrole dispersion liquid, 6 h of magnetic agitation.Transposition is in evaporating dish, in 80
After being dried overnight at DEG C, it is uniform to take out grinding.It is pyrolyzed in tube furnace.1) 300 are risen to from room temperature with the rate of 1 DEG C/min
DEG C, keep the temperature 3 h.2) 900 DEG C are risen to the rate of 10 DEG C/min, keeps the temperature 2 h.Cooled to room temperature obtains black powder.
The product X-ray powder diffraction result is as shown in Figure 1.As shown in XRD spectrum in Fig. 2, all diffraction maximums can be with Co9S8Standard
Peak (PDF#75-2023) is corresponding.Show that the sample has apparent core-shell structure by HRTEM Fig. 4, i.e. outer layer is doping
Carbon-coating, internal layer Co9S8 Core.Pass through electro-chemical test (Fig. 6), it was demonstrated that the material has good electrochemistry HER and OER
Energy.
Embodiment 3
Ammonium persulfate ((NH4) is weighed respectively2S2O8) 4.2 g are dissolved in 40 mL deionized waters, (0 ~ 5 DEG C) magnetic under conditions of ice bath
Power stirring, is slowly inwardly added dropwise 620 μ L pyrrole monomers, keeps condition of ice bath, continues 5 h of magnetic agitation.It is transferred to evaporating dish
In, dry 24 h at 80 DEG C.It takes out, grinding is scattered in 10 mL deionized waters, by nickel chloride (NiCl2·6H2O) 1.093
G is dissolved in 10 mL deionized waters, is added dropwise in above-mentioned polypyrrole dispersion liquid, 6 h of magnetic agitation.Transposition is in evaporating dish, in 80
After being dried overnight at DEG C, it is uniform to take out grinding.It is pyrolyzed in tube furnace.1) 300 are risen to from room temperature with the rate of 1 DEG C/min
DEG C, keep the temperature 3 h.2) 900 DEG C are risen to the rate of 10 DEG C/min, keeps the temperature 2 h.Cooled to room temperature obtains black powder.
50 mg of the sample will be accurately weighed to be scattered in 1.0 M HCL aqueous solutions, 48 h of magnetic agitation.Centrifugation, it is dry, obtain product.
The product X-ray powder diffraction result is as shown in Figure 1.As shown in XRD spectrum in Fig. 3, all diffraction maximums can be with Ni3S2Standard
Peak (PDF#44-1418) and NiS base peak (PDF#12-0041) are corresponding.Through Fig. 5, HRTEM, it can be deduced that the product has three
Layer structure, i.e. outermost layer are carbon-coating, and middle layer is NiS layers, innermost layer Ni3S2Layer.Pass through electro-chemical test, it was demonstrated that the material
With good electrochemistry HER, OER and ORR performance.
Embodiment 4
Ammonium persulfate ((NH4) is weighed respectively2S2O8) 4.2 g are dissolved in 40 mL deionized waters, (0 ~ 5 DEG C) magnetic under conditions of ice bath
Power stirring, is slowly inwardly added dropwise 620 μ L pyrrole monomers, keeps condition of ice bath, continues 5 h of magnetic agitation.It is transferred to evaporating dish
In, dry 24 h at 80 DEG C.It takes out, grinding is scattered in 10 mL deionized waters, by nickel chloride (NiCl2·6H2O) 1.093
G is dissolved in 10 mL deionized waters, is added dropwise in above-mentioned polypyrrole dispersion liquid, 6 h of magnetic agitation.Transposition is in evaporating dish, in 80
After being dried overnight at DEG C, it is uniform to take out grinding.It is pyrolyzed in tube furnace.1) 300 are risen to from room temperature with the rate of 1 DEG C/min
DEG C, keep the temperature 3 h.2) 700 DEG C are risen to the rate of 10 DEG C/min, keeps the temperature 2 h.Cooled to room temperature obtains black powder.
The product X-ray powder diffraction result is as shown in Fig. 1 embodiment 4.Shown such as Fig. 1, all diffraction maximums can be with Ni3S2Standard
Peak (PDF#44-1418) is corresponding.Illustrate that last carburizing temperature can't mutually impact its object.By electro-chemical test,
Prove that the material has good electrochemistry HER, OER and ORR performance.
Embodiment 5
Ammonium persulfate ((NH is weighed respectively4)2S2O8) 4.2 g are dissolved in 40 mL deionized waters, (0 ~ 5 DEG C) magnetic under conditions of ice bath
Power stirring, is slowly inwardly added dropwise 620 μ L pyrrole monomers, keeps condition of ice bath, continues 5 h of magnetic agitation.It is transferred to evaporating dish
In, dry 24 h at 80 DEG C.It takes out, grinding is scattered in 10 mL deionized waters, by nickel chloride (NiCl2·6H2O) 2.19 g
10 mL deionized waters are dissolved in, are added dropwise in above-mentioned polypyrrole dispersion liquid, 6 h of magnetic agitation.Transposition is in evaporating dish, in 80 DEG C
Under be dried overnight after, it is uniform to take out grinding.It is pyrolyzed in tube furnace.1) 300 are risen to from room temperature with the rate of 1 DEG C/min
DEG C, keep the temperature 3 h.2) 900 DEG C are risen to the rate of 10 DEG C/min, keeps the temperature 2 h.Cooled to room temperature obtains black powder.
The product X-ray powder diffraction result is as shown in Figure 1.Spectral line is implemented shown in 5 as shown in figure 1, and all diffraction maximums can be with Ni3S2Mark
Quasi- peak (PDF#44-1418) is corresponding.Illustrate that the amount that nickel chloride is added can't mutually impact its object.It is surveyed by electrochemistry
Examination, it was demonstrated that the material has good electrochemistry HER, OER and ORR performance.
Claims (4)
1. a kind of nanosphere of the doped carbon encapsulation transient metal sulfide applied to electro-catalysis, chemical formula are as follows: M x S y @NOSC,
M be Fe, Co or Ni,x、yFor sulfide coefficient, value range is respectively as follows: 9≤x≤ 1,9≤y≤1.
2. the preparation method described in claim 1 applied to the nanosphere of the doped carbon encapsulation transient metal sulfide of electro-catalysis,
It is characterized by comprising following steps: weighing oxidant, is dissolved in deionized water, high polymer monomer is added dropwise and is polymerize, does
Transistion metal compound is added after dry to be chelated, dry, grinding carries out multistep sintering, after be cooled to room temperature, product is ground
Obtain product.
3. preparation method as described in claim 1, which is characterized in that the oxidant is ammonium persulfate or iron chloride；
The high polymer monomer is pyrroles, aniline or dopamine；The transistion metal compound be its oxide, chloride, nitrate,
The mixture of any one compound or multiple compounds composition in carbonate, oxalates.
4. preparation method as described in claim 1, which is characterized in that the sintering temperature is 600 ~ 1000 DEG C, sintering time
For 10 ~ 30 h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110028107A (en) * | 2019-03-19 | 2019-07-19 | 青岛科技大学 | The preparation and application of transient metal sulfide nanosphere |
| CN113694952A (en) * | 2021-08-24 | 2021-11-26 | 青岛科技大学 | Sulfur-containing vacancy NiS quantum dot/S, N and O co-doped carbon electrode material and preparation method thereof |
| CN114016053A (en) * | 2021-12-10 | 2022-02-08 | 福州大学 | Method for improving stability of transition metal sulfide catalyst |
| CN116060074A (en) * | 2021-11-01 | 2023-05-05 | 中自环保科技股份有限公司 | Catalytic carrier for electrochemical reaction and preparation method thereof |
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| CN110028107A (en) * | 2019-03-19 | 2019-07-19 | 青岛科技大学 | The preparation and application of transient metal sulfide nanosphere |
| CN113694952A (en) * | 2021-08-24 | 2021-11-26 | 青岛科技大学 | Sulfur-containing vacancy NiS quantum dot/S, N and O co-doped carbon electrode material and preparation method thereof |
| CN113694952B (en) * | 2021-08-24 | 2023-09-01 | 乌海瑞森新能源材料有限公司 | Sulfur-vacancy-containing NiS quantum dot/S, N, O co-doped carbon electrode material and preparation method thereof |
| CN116060074A (en) * | 2021-11-01 | 2023-05-05 | 中自环保科技股份有限公司 | Catalytic carrier for electrochemical reaction and preparation method thereof |
| CN114016053A (en) * | 2021-12-10 | 2022-02-08 | 福州大学 | Method for improving stability of transition metal sulfide catalyst |
| CN114016053B (en) * | 2021-12-10 | 2023-11-14 | 福州大学 | Method for improving stability of transition metal sulfide catalyst |
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