CN115110113B - Rod-shaped Co 2 C-MoN composite material and preparation method and application thereof - Google Patents
Rod-shaped Co 2 C-MoN composite material and preparation method and application thereof Download PDFInfo
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- CN115110113B CN115110113B CN202210631531.5A CN202210631531A CN115110113B CN 115110113 B CN115110113 B CN 115110113B CN 202210631531 A CN202210631531 A CN 202210631531A CN 115110113 B CN115110113 B CN 115110113B
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- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 54
- 239000002243 precursor Substances 0.000 claims abstract description 31
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 27
- 239000006260 foam Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 150000001868 cobalt Chemical class 0.000 claims description 11
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 11
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 64
- 239000004202 carbamide Substances 0.000 abstract description 64
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 23
- 239000001257 hydrogen Substances 0.000 abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 23
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 238000000354 decomposition reaction Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000007864 aqueous solution Substances 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 239000012670 alkaline solution Substances 0.000 abstract description 5
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010411 electrocatalyst Substances 0.000 abstract description 4
- 238000003837 high-temperature calcination Methods 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 18
- 239000003792 electrolyte Substances 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 16
- 238000005868 electrolysis reaction Methods 0.000 description 12
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—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
-
- 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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- 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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
Abstract
The invention provides a bar-shaped Co 2 C-MoN composite material, and a preparation method and application thereof. The preparation method of the rod-shaped composite material comprises the steps of placing foam nickel in a mixed solution for hydrothermal reaction to prepare a cobalt molybdate precursor material; and then, high-temperature calcination is carried out by a high-temperature calcination method to obtain the composite material. The composite material prepared by the method has excellent catalytic performance on urea oxidation reaction of an anode and hydrogen evolution reaction of a cathode in alkaline solution containing urea; on this basis, a double-electrode electrolytic cell system was constructed. At a current density of 50 mA.cm ‑2 When the voltage required for the overall urea aqueous solution decomposition was 1.507V, the voltage required for the overall urea aqueous solution decomposition was 171mV lower than that required for the overall urea aqueous solution decomposition. In addition, the prepared catalyst not only can catalyze hydrogen production with high efficiency, but also can treat urea in wastewater effectively. Therefore, it would be a very promising green electrocatalyst.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a bar-shaped Co 2 C-MoN composite material, and a preparation method and application thereof.
Background
In order to develop clean new energy, new alternative energy sources such as nuclear energy, solar energy, wind energy, hydrogen energy and the like are developed according to local conditions in various countries of the world, wherein the hydrogen energy is of great concern. The development and utilization of hydrogen energy is the first problem to be solved is the low-cost, large-scale hydrogen production. The preparation method of the hydrogen comprises the steps of water electrolysis hydrogen production, fossil energy hydrogen production, biomass hydrogen production and the like, wherein the hydrogen prepared by water electrolysis hydrogen production has higher purity and is widely applied in industry. The electrolyzed water includes a Hydrogen Evolution Reaction (HER) and an Oxygen Evolution Reaction (OER). In theory, electrolysis of water can be performed at a voltage exceeding 1.229V, but in actual electrolysis, a higher voltage is required for water separation due to the existence of overpotential in the hydrogen and oxygen generation reaction, particularly complex multi-electron steps in OER. Therefore, urea Oxidation Reaction (UOR) with lower oxidation potential is adopted to replace OER, thereby reducingLow overpotential during the reaction. In order to further reduce the reaction overpotential, a suitable electrocatalyst still needs to be developed. Currently, noble metals Pt/C and IrO 2 Has been demonstrated to have excellent catalytic effects on HER and OER, respectively. However, their high cost and low storage capacity are significant obstacles to large-scale application production.
In recent years, various non-noble metal catalysts, such as transition metal oxides, have been studied, which have advantages of being abundant in reserves, low in price, easy to prepare, environmentally friendly, and the like. The transition metal element such as Mn, fe, co, ni has multiple valence states, and can form oxides having various crystal structures, which have a good catalytic effect on oxygen evolution reaction but poor catalytic effect on hydrogen evolution reaction.
Based on the drawbacks of the current non-noble metal catalysts, improvements are needed.
Disclosure of Invention
In view of this, the present invention provides a rod-like Co 2 The C-MoN composite material and the preparation method and application thereof are used for solving or partially solving the problem of overlarge energy consumption in the prior art.
In a first aspect, the present invention provides a Co rod 2 The preparation method of the C-MoN composite material comprises the following steps: adding cobalt salt into water to obtain a first solution; adding molybdate into water to obtain a second solution; mixing the first solution and the second solution to obtain a mixed solution; placing the foam nickel into the mixed solution, and reacting for 4-8 hours at 150-170 ℃ to obtain a precursor material; respectively placing the precursor material and dicyandiamide in a tube furnace, heating to 500-700 ℃ under the protection of inert gas, and keeping for 1-3 h to obtain Co 2 C-MoN composite material.
In a second aspect, the invention also provides a rod-shaped Co 2 The C-MoN composite material is prepared by adopting the preparation method.
In a third aspect, the invention also provides the rod-shaped Co 2 The application of the C-MoN composite material as a catalyst.
A rod-shaped Co of the invention 2 C-MoN composite materialCompared with the prior art, the preparation method and the catalytic performance of the material have the following beneficial effects:
the rod-shaped Co of the invention 2 The preparation method of the C-MoN composite material comprises the steps of placing foam nickel in a mixed solution for hydrothermal reaction to prepare a cobalt molybdate precursor material; then the cobalt molybdate precursor material and dicyandiamide are respectively put into a tube furnace to be calcined at high temperature by a high-temperature calcination method, thus obtaining Co 2 C-MoN composite material. Co prepared by the method 2 The C-MoN composite material has excellent catalytic performance on urea oxidation reaction of an anode and hydrogen evolution reaction of a cathode in an alkaline solution containing urea; further, the target product (Co 2 C/MoN-600/NF) has optimal catalytic performance on the urea oxidation reaction of the anode and the hydrogen evolution reaction of the cathode in an alkaline solution containing urea. On the basis, a double-electrode electrolytic cell system (Co 2 C/MoN-600/NF‖Co 2 C/Mon-600/NF). At a current density of 50 mA.cm -2 When the voltage required for the overall urea aqueous solution decomposition was 1.507V (vs RHE), the voltage required for the overall urea aqueous solution decomposition was 171mV lower than that required for the overall urea aqueous solution decomposition. In addition, the prepared catalyst not only can catalyze hydrogen production with high efficiency, but also can treat urea in wastewater effectively. Therefore, it would be a very promising green electrocatalyst.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is evident that the drawings in the following description are only some embodiments of the present invention and that other drawings may be obtained from these drawings without inventive effort for a person of ordinary skill in the art.
FIG. 1 shows a rod-like Co obtained in example 1 of the present invention 2 X-ray diffraction pattern of C/MoN-600/NF material;
FIG. 2 is a rod-like Co obtained in example 1 of the present invention 2 X-ray photoelectron spectrum of C/MoN-600/NF material;
FIG. 3 shows the present inventionCo in the form of rod prepared in example 1 2 Scanning Electron Microscope (SEM) images of C/MoN-600/NF materials at different magnification;
FIG. 4 shows a rod-like Co obtained in example 1 of the present invention 2 Transmission Electron Microscope (TEM) images of C/MoN-600/NF materials at different magnifications;
FIG. 5 shows a rod-like Co obtained in example 1 of the present invention 2 LSV curve comparison graphs of C/MoN-600/NF materials in three electrolytes;
FIG. 6 shows a precursor material (CoMoO) prepared in example 1 of the present invention 6 ·0.9H 2 O/NF)、Co 2 LSV curve comparison graphs of C/MoN-600/NF, bare foam Nickel (NF) and Pt/C/NF respectively in 1M KOH electrolyte;
FIG. 7 shows Co prepared in examples 1 to 5 of the present invention 2 LSV curve contrast graphs of HER of the C/MoN composite material in 1M KOH electrolyte;
FIG. 8 shows a precursor material (CoMoO) prepared in example 1 of the present invention 6 ·0.9H 2 O/NF)、Co 2 C/MoN-600/NF, bare foam Nickel (NF), pt/C/NF respectively in the Tafel plot corresponding to electrolytic HER;
FIG. 9 shows Co prepared in examples 1 to 5 of the present invention 2 Tafel graphs corresponding to the C/MoN composite materials in the electrolysis HER respectively;
FIG. 10 is a graph showing the Co produced in example 1 of the present invention 2 LSV graphs of HER of C/MoN-600/NF material at different sweep rates in 1M KOH electrolyte;
FIG. 11 is a graph showing the Co produced in example 1 of the present invention 2 Multi-step voltage step plot for C/MoN-600/NF as catalyst;
FIG. 12 is Co obtained in example 1 of the present invention 2 Amperometric-time curve (i-t) plot of C/Mon-600/NF after 25h electrolysis at-176 mV in 1M KOH electrolyte;
FIG. 13 is Co obtained in example 1 of the present invention 2 LSV curves for C/MoN-600/NF in 1M KOH (oxygen evolution reaction (OER)), 0.5M urea, 1M KOH, and 0.5M urea (urea oxidation reaction (UOR)), respectively;
FIG. 14 shows a precursor material (CoMoO) prepared in example 1 of the present invention 6 ·0.9H 2 O/NF)、Co 2 C/MoN-600/NF, bare foam Nickel (NF), irO 2 LSV curve comparison of UOR in 1M KOH electrolyte containing 0.5M urea;
FIG. 15 shows Co prepared in examples 1 to 5 of the present invention 2 LSV curve comparison graphs of UOR for the C/MoN composites in 1M KOH electrolyte containing 0.5M urea, respectively;
FIG. 16 shows a precursor material (CoMoO) prepared in example 1 of the present invention 6 ·0.9H 2 O/NF)、Co 2 C/MoN-600/NF, bare foam Nickel (NF), irO 2 Respectively carrying out Tafel graphs corresponding to UOR in urea electrolysis;
FIG. 17 shows Co prepared in examples 1 to 5 of the present invention 2 C/MoN composite material respectively has Tafel curves corresponding to UOR in urea electrolysis;
FIG. 18 is Co in example 1 of the present invention 2 LSV plot of UOR at different sweep rates for C/Mon-600/NF in 1M KOH solution containing 0.5M urea;
FIG. 19 is Co in a 1M KOH electrolyte solution containing 0.5M Urea 2 A multi-step voltage step plot for a C/MoN-600/NF catalyst;
FIG. 20 is Co in a 1M KOH electrolyte containing 0.5M Urea 2 LSV contrast curve graph of C/MoN-600/NF after 3000 circles of cyclic voltammetry scanning;
FIG. 21 shows a precursor material (CoMoO) prepared in example 1 of the present invention 6 ·0.9H 2 O/NF)、Co 2 An electric double layer capacitance value of C/MoN-600/NF, relative electrochemically active surface area of bare foam Nickel (NF);
FIG. 22 shows Co prepared in examples 1 to 5 of the present invention 2 Electric double layer capacitance value of relative electrochemically active surface area of the C/MoN composite;
FIG. 23 shows a precursor material (CoMoO) prepared in example 1 of the present invention 6 ·0.9H 2 O/NF)、Co 2 Electrochemical Impedance Spectroscopy (EIS) contrast plots of C/Mon-600/NF, bare foam Nickel (NF) in 1M KOH solution with 0.5M urea, respectively;
FIG. 24 shows Co prepared in examples 1 to 5 of the present invention 2 Electrochemical Impedance Spectroscopy (EIS) plots of the C/MoN composites in 1M KOH solution with 0.5M urea, respectively;
FIG. 25 is Co in example 1 2 C/MoN-600/NF is used as an anode and a cathode respectively to form a structural schematic diagram of the double-electrode system;
FIG. 26 is Co 2 C/MoN-600/NF‖Co 2 Polarization curve comparison plot of C/Mon-600/NF in 1M KOH solution with 0.5M urea and 1M KOH solution without urea;
FIG. 27 is CoMoO 6 ·0.9H 2 O/NF‖CoMoO 6 ·0.9H 2 O/NF、Co 2 C/MoN-600/NF‖Co 2 C/MoN-600/NF、Pt/C/NF‖IrO 2 Polarization curve comparison of/NF in 1M KOH solution containing 0.5M urea;
FIG. 28 is Co at a cell voltage of 1.5V 2 C/MoN-600/NF‖Co 2 Amperometric-time curve (i-t) for C/MoN-600/NF electrolyzed urea.
Detailed Description
The following description of the embodiments of the present invention will be made in detail and with reference to the embodiments of the present invention, but it should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
The embodiment of the application provides a bar-shaped Co 2 The preparation method of the C-MoN composite material comprises the following steps:
s1, adding cobalt salt into water to obtain a first solution;
s2, adding molybdate into water to obtain a second solution;
s3, mixing the first solution and the second solution to obtain a mixed solution;
s4, placing the foam nickel into the mixed solution, and reacting for 4-8 hours at 150-170 ℃ to obtain a precursor material;
s5, respectively placing the precursor material and dicyandiamide in a tube furnace, heating to 500-700 ℃ under the protection of inert gas, and keeping for 1-3 h to obtain Co 2 C-MoN composite material.
Rod-shaped Co of the present application 2 The preparation method of the C-MoN composite material comprises the steps of placing foam nickel in a mixed solution for hydrothermal reaction to prepare a cobalt molybdate precursor material; then the cobalt molybdate precursor material and dicyandiamide are respectively put into a tube furnace to be calcined at high temperature by a high-temperature calcination method, thus obtaining Co 2 C-MoN composite material. Co prepared by the method 2 The C-MoN composite material has excellent catalytic performance on urea oxidation reaction of an anode and hydrogen evolution reaction of a cathode in an alkaline solution containing urea; further, the target product (Co 2 C/Mon-600/NF) has optimal catalytic performance on the urea oxidation reaction of the anode and the hydrogen evolution reaction of the cathode in an alkaline solution containing urea. On the basis, a double-electrode electrolytic cell system (Co 2 C/MoN-600/NF‖Co 2 C/Mon-600/NF). At a current density of 50 mA.cm -2 When the voltage required for the overall urea aqueous solution decomposition was 1.507V (vs RHE), the voltage required for the overall urea aqueous solution decomposition was 171mV lower than that required for the overall urea aqueous solution decomposition. In addition, the prepared catalyst not only can catalyze hydrogen production with high efficiency, but also can treat urea in wastewater effectively. Therefore, it would be a very promising green electrocatalyst.
In some embodiments, the cobalt salt comprises at least one of cobalt sulfate, cobalt nitrate, cobalt chloride.
In some embodiments, the molybdate comprises at least one of ammonium molybdate, sodium molybdate, potassium molybdate, ammonium heptamolybdate.
In some embodiments, in the step of adding cobalt salt to water, the molar volume ratio of cobalt salt to water is (0.5-2) mmol (15-25) mL;
and/or, in the step of adding molybdate to water, the molar volume ratio of molybdate to water is (0.1 to 0.2) mmol (5 to 15) mL;
and/or the molar mass ratio of cobalt salt to dicyandiamide is (0.5-2) mmol (0.3-0.7) g.
In some embodiments, the precursor material and dicyandiamide are respectively placed in a tube furnace, and under the protection of inert gas, the temperature is raised to 500-700 ℃ at the speed of 3-7 ℃/min and kept for 1-3 h, thus obtaining Co 2 C-MoN composite material.
In particular, the inert gas may be a noble gas or nitrogen; respectively placing the precursor material and dicyandiamide into two porcelain boats, then placing the porcelain boats into a tube furnace for calcination, and naturally cooling to obtain Co 2 C-MoN composite material.
In some embodiments, prior to placing the nickel foam in the mixed solution, further comprising ultrasonically cleaning the nickel foam with hydrochloric acid, acetone, ultrapure water, and ethanol in that order.
In some embodiments, the foamed nickel is placed in a mixed solution, reacted for 4 to 8 hours at 150 to 170 ℃, washed, and then dried at 40 to 80 ℃ to obtain the precursor material.
Based on the same inventive concept, the embodiment of the application also provides a rod-shaped Co 2 The C-MoN composite material is prepared by adopting the preparation method.
Based on the same inventive concept, the embodiment of the application also provides the rod-shaped Co 2 The application of the C-MoN composite material as a catalyst.
Specifically, the rod-shaped Co of the present application 2 The C-MoN composite material can be used as a catalyst for efficiently catalyzing hydrogen production, and can also be used for effectively catalyzing urea decomposition in wastewater.
The rod-like Co of the present application is further described in the following by way of specific examples 2 The preparation method of the C-MoN composite material is further described in this section in connection with specific examples, but should not be construed as limiting the invention. The technical means employed in the examples are conventional means well known to those skilled in the art, unless specifically stated. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1
The embodiment of the application provides a bar-shaped Co 2 The preparation method of the C-MoN composite material comprises the following steps ofThe method comprises the following steps:
s1, sequentially adopting dilute hydrochloric acid solution (the mass concentration is 5%), acetone, ultrapure water and ethanol to cut out foam nickel (4 multiplied by 2 cm) 2 I.e. 4cm in length and 2cm in width) is subjected to ultrasonic cleaning and vacuum drying for later use;
s2, dissolving 1mmol of cobalt nitrate in 20mL of deionized water, and uniformly dispersing by ultrasonic to obtain a first solution;
s3, dissolving 0.15mmol of ammonium heptamolybdate in 10mL of deionized water, and uniformly dispersing by ultrasonic to obtain a second solution;
s3, adding the second solution into the first solution, and stirring for 30min to uniformly mix the second solution and the first solution to obtain a mixed solution;
s4, placing the mixed solution into a 50mL polytetrafluoroethylene lining reaction kettle, then adding the foam nickel in the step S1, reacting for 6 hours at 160 ℃, respectively washing with water and absolute ethyl alcohol after the reaction is finished, and then vacuum drying at 60 ℃ to obtain a precursor material;
s5, respectively placing the precursor material in the step S4 and 0.5g dicyandiamide into two porcelain boats, then placing the porcelain boats into a tube furnace, heating to 600 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, calcining for 2h and naturally cooling to finally obtain a target product Co 2 C-MoN composite (denoted Co 2 C/MoN-600/NF)。
Example 2
The embodiment of the application provides a bar-shaped Co 2 The preparation method of the C-MoN composite material is the same as in example 1, except that the C-MoN composite material is calcined at 500 ℃ for 2 hours in step S5, and the rest of the process parameters are the same as in example 1, so as to prepare Co 2 The C-MoN composite material is denoted as Co 2 C/MoN-500/NF。
Example 3
The embodiment of the application provides a bar-shaped Co 2 The preparation method of the C-MoN composite material is the same as in example 1, except that the C-MoN composite material is calcined at 550 ℃ for 2 hours in step S5, and the rest of the process parameters are the same as in example 1, so as to prepare Co 2 The C-MoN composite material is denoted as Co 2 C/MoN-550/NF。
Example 4
Implementation of the present applicationExample provided rod Co 2 The preparation method of the C-MoN composite material is the same as in example 1, except that the C-MoN composite material is calcined at 650 ℃ for 2 hours in step S5, and the rest of the process parameters are the same as in example 1, so as to prepare Co 2 The C-MoN composite material is denoted as Co 2 C/MoN-650/NF。
Example 5
The embodiment of the application provides a bar-shaped Co 2 The preparation method of the C-MoN composite material is the same as in example 1, except that the C-MoN composite material is calcined at 700 ℃ for 2 hours in step S5, and the rest of the process parameters are the same as in example 1, so as to prepare Co 2 The C-MoN composite material is denoted as Co 2 C/MoN-700/NF。
Performance testing
FIG. 1 is a rod-like Co obtained in example 1 2 X-ray diffraction (XRD) pattern for C/MoN-600/NF material. In FIG. 1, ni, co 2 C. The XRD pattern of MoN is located at Co 2 Under the C/MoN-600/NF material pattern.
As can be seen from FIG. 1, co 2 C/Mon-600/NF was successfully synthesized.
FIG. 2 is a rod-like Co obtained in example 1 2 X-ray photoelectron spectroscopy (XPS) of C/MoN-600/NF materials, wherein: in fig. 2, (a) high resolution peak splitting spectrum of Co 2 p; (b) high resolution peak splitting spectrum of Mo 3 d; (c) high resolution peak splitting spectra of N1 s; (d) high resolution peak splitting spectra of C1 s; as can be seen, co 2 C and MoN are present simultaneously.
FIG. 3 is a rod-like Co obtained in example 1 2 Scanning Electron Microscope (SEM) images of C/MoN-600/NF materials at different magnifications. As can be seen from fig. 3, the prepared material exhibits a rod-like structure.
FIG. 4 is a rod-like Co obtained in example 1 2 Transmission Electron Microscope (TEM) pictures of the C/MoN-600/NF material under different magnification conditions; fig. 4 (b) is an enlarged view of (a) at the dashed line box.
As can be seen from FIG. 4, the rod-like Co prepared in example 1 2 The surface of the rod-shaped structure of the C/MoN-600/NF material is provided with nano particles with the diameter of about 50 nm.
FIG. 5 shows the three electrodesCo in the form of rod prepared in example 1 in the system 2 LSV curve comparison plot of Hydrogen Evolution Reaction (HER) in 1M KOH solution, 0.5M urea (i.e., urea), 1M KOH and 0.5M urea, respectively, of electrolyte at a scan rate of 5mV/s with C/MoN-600/NF material as working electrode, hg/HgO electrode as reference electrode, carbon rod as counter electrode.
As can be seen from fig. 5, the two polarization curves in 1M KOH, and 0.5M urea electrolyte substantially coincide, indicating that urea has little effect on HER performance.
FIG. 6 shows the precursor materials (CoMoO) prepared in step S4 of example 1 in a three-electrode system 6 ·0.9H 2 O/NF), co prepared in example 1 2 LSV curve comparison of HER in 1M KOH electrolyte at 5mV/s with 5.0mg of Pt/C (20 wt%) powder from Michelin Corp, 200. Mu.L of isopropanol, 32. Mu.L of naphthol and 768. Mu.L of deionized water after mixing well, 200. Mu.L of the mixture was dropped onto foam nickel (0.5 cm. Times.0.5 cm) as working electrode, hg/HgO electrode as reference electrode, carbon rod as counter electrode, and HER in 1M KOH electrolyte.
FIG. 7 shows Co prepared in examples 1 to 5 2 LSV curve comparison plots of HER in 1M KOH electrolyte for the C/MoN composites, respectively.
As can be seen from FIGS. 6 to 7, co prepared in example 1 2 The HER performance of the C/MoN-600/NF material is closest to Pt/C/NF.
FIG. 8 shows the precursor materials (CoMoO) prepared in step S4 of example 1 in a three-electrode system 6 ·0.9H 2 O/NF), co prepared in example 1 2 C/MoN-600/NF, bare foam Nickel (NF), pt/C/NF as working electrode, hg/HgO electrode as reference electrode, carbon rod as counter electrode, and Tafel curve corresponding to electrolytic HER at a scanning rate of 5 mV/s.
FIG. 9 shows Co prepared in examples 1 to 5 2 C/MoN composites have corresponding Tafel curves in electrolytic HER, respectively.
As can be seen from FIGS. 8 to 9, co prepared in example 1 2 Tafil slope of C/MoN-600/NFThe rate is closest to Pt/C/NF, indicating its excellent catalytic kinetics.
FIG. 10 shows a rod-like Co prepared in example 1 in a three-electrode system 2 The LSV curve of HER in 1M KOH electrolyte at different sweeping speeds is prepared by using a C/MoN-600/NF material as a working electrode, a Hg/HgO electrode as a reference electrode and a carbon rod as a counter electrode; it can be seen that the sweep rate and current have good linear relationship, indicating Co 2 C/MoN-600/NF has higher charge and mass transfer efficiency in the catalytic process.
FIG. 11 shows a rod-like Co prepared in example 1 in a three-electrode system 2 A multi-step voltage step curve contrast diagram with a C/MoN-600/NF material as a working electrode, an Hg/HgO electrode as a reference electrode and a carbon rod as a counter electrode; it can be seen that the current increases with the voltage, can quickly respond and remain stable, indicating Co 2 C/MoN-600/NF has good mass transfer performance.
FIG. 12 shows a rod-like Co prepared in example 1 in a three-electrode system 2 An ampere-time curve (i-t) diagram of a C/MoN-600/NF material as a working electrode, an Hg/HgO electrode as a reference electrode, a carbon rod as a counter electrode after 25h electrolysis in a 1M KOH solution environment at a voltage of-176 mV at a scanning rate of 5 mV/s; as can be seen, co 2 C/Mon-600/NF has good long-term electrochemical stability.
FIG. 13 shows a rod-like Co prepared in example 1 in a three-electrode system 2 LSV curves in 1M KOH (oxygen evolution reaction (OER)), 0.5M urea, 1M KOH and 0.5M urea (urea oxidation reaction (UOR)) solutions at a scan rate of 5mV/s respectively were plotted against the LSV curves with the C/MoN-600/NF material as the working electrode, the Hg/HgO electrode as the reference electrode, and the carbon rod as the counter electrode.
As can be seen from fig. 13, UOR is much lower than the voltage required for OER.
FIG. 14 shows the precursor materials (CoMoO) prepared in step S4 of example 1 in a three-electrode system 6 ·0.9H 2 O/NF), co prepared in example 1 2 C/MoN-600/NF, bare foam Nickel (NF), irO 2 /NF (from 5.0mg available from Michelin)IrO of company 2 (20 wt%) powder, 200. Mu.L of isopropanol, 32. Mu.L of naphthol and 768. Mu.L of deionized water were mixed uniformly, and 200. Mu.L of the mixture was dropped onto foamed nickel (0.5 cm. Times.0.5 cm) to obtain a LSV curve comparison chart of UOR in 1M KOH electrolyte containing 0.5M urea at a scanning rate of 5mV/s with Hg/HgO electrode as a reference electrode and carbon rod as a counter electrode.
FIG. 15 shows Co prepared in examples 1 to 5 in a three-electrode system 2 LSV curve comparison graph of UOR in 1M KOH electrolyte containing 0.5M urea with C/MoN composite material as working electrode, hg/HgO electrode as reference electrode, carbon rod as counter electrode and scanning rate of 5 mV/s.
As can be seen from FIGS. 14 to 15, co prepared in example 1 2 The UOR catalytic effect of C/MoN-600/NF is optimal.
FIG. 16 shows the precursor materials (CoMoO) prepared in step S4 of example 1 in a three-electrode system 6 ·0.9H 2 O/NF), co prepared in example 1 2 C/MoN-600/NF, bare foam Nickel (NF), irO 2 And (3) taking/NF as a working electrode, taking an Hg/HgO electrode as a reference electrode, taking a carbon rod as a counter electrode, and taking a Tafel curve corresponding to UOR in urea electrolysis at a scanning rate of 5 mV/s.
FIG. 17 shows Co prepared in examples 1 to 5, respectively, in a three-electrode system 2 The C/MoN composite material is used as a working electrode, the Hg/HgO electrode is used as a reference electrode, the carbon rod is used as a counter electrode, and the Tafel curves corresponding to UOR in urea electrolysis are respectively obtained at a scanning rate of 5 mV/s.
As can be seen from FIGS. 16 to 17, co in example 1 2 The C/MoN-600/NF has fast charge transfer dynamics and good catalytic performance.
FIG. 18 shows a rod-like Co prepared in example 1 in a three-electrode system 2 LSV graph of UOR at different sweep rates in 1M KOH solution containing 0.5M urea with C/MoN-600/NF material as working electrode, hg/HgO electrode as reference electrode, carbon rod as counter electrode.
As can be seen from FIG. 18, co 2 C/Mon-600/NF has higherCharge and mass transport efficiency.
FIG. 19 is a rod-like Co prepared in example 1 in a three-electrode system 2 C/MoN-600/NF material was used as the working electrode, hg/HgO electrode was used as the reference electrode, carbon rod was used as the counter electrode, and a multi-step voltage step curve was obtained in 1M KOH electrolyte containing 0.5M urea at a scan rate of 5 mV/s. As can be seen from FIG. 19, co 2 The C/MoN-600/NF has good conductivity and mass transfer performance.
FIG. 20 shows a rod-like Co prepared in example 1 in a three-electrode system 2 C/MoN-600/NF material is used as a working electrode, hg/HgO electrode is used as a reference electrode, a carbon rod is used as a counter electrode, and an LSV comparison curve before and after 3000 circles of cyclic voltammetry scanning is carried out in a 1M KOH solution environment containing 0.5M urea at a scanning rate of 5 mV/s; as can be seen from FIG. 20, co 2 C/MoN-600/NF has better electrochemical stability.
FIG. 21 shows the precursor material (CoMoO) prepared in step S4 of example 1 6 ·0.9H 2 O/NF), co prepared in example 1 2 Electric double layer capacitance value of C/Mon-600/NF, relative electrochemically active surface area of bare foam Nickel (NF).
FIG. 22 shows Co prepared in examples 1 to 5 2 Electric double layer capacitance value of the relative electrochemically active surface area of the C/MoN composite.
As can be seen from FIGS. 21 to 22, co 2 C/Mon-600/NFF has the largest double layer capacitance (C dl ) The value indicates that the catalyst has the largest electrochemical active area.
FIG. 23 shows the precursor materials (CoMoO) prepared in step S4 of example 1 in a three-electrode system 6 ·0.9H 2 O/NF), co prepared in example 1 2 C/MoN-600/NF, bare foam Nickel (NF) as working electrode, hg/HgO electrode as reference electrode, carbon rod as counter electrode, and Electrochemical Impedance Spectroscopy (EIS) at 5mV/s scan rate in 1M KOH solution containing 0.5M urea.
FIG. 24 shows Co prepared in examples 1 to 5, respectively, in a three-electrode system 2 C/MoN composite material as materialThe working electrode, hg/HgO electrode as reference electrode, carbon rod as counter electrode, and Electrochemical Impedance Spectroscopy (EIS) at a scan rate of 5mV/s in 1M KOH solution containing 0.5M urea.
As can be seen from FIGS. 23 to 24, co 2 C/Mon-600/NF has the smallest resistance, meaning a faster electron transfer rate.
FIG. 25 is Co in example 1 2 C/Mon-600/NF was used as anode and cathode, respectively, to form a two-electrode system (Co 2 C/MoN-600/NF‖Co 2 C/Mon-600/NF).
FIG. 26 is Co 2 C/MoN-600/NF‖Co 2 Polarization curve comparison plot of C/Mon-600/NF in 1M KOH solution with 0.5M urea and 1M KOH solution without urea; the results show that the same current density is achieved with a urea-containing two-electrode system requiring a much lower cell voltage than a system without urea.
The precursor material CoMoO prepared in example 1 was prepared according to the above procedure 6 ·0.9H 2 O/NF is used as anode and cathode respectively to form a double-electrode system CoMoO 6 ·0.9H 2 O/NF‖CoMoO 6 ·0.9H 2 O/NF; pt/C/NF, irO 2 the/NF is used as anode and cathode respectively to form a double-electrode system Pt/C/NF II IrO 2 /NF。
FIG. 27 is CoMoO 6 ·0.9H 2 O/NF‖CoMoO 6 ·0.9H 2 O/NF、Co 2 C/MoN-600/NF‖Co 2 C/MoN-600/NF、Pt/C/NF‖IrO 2 Polarization curve comparison of/NF in 1M KOH solution containing 0.5M urea; as can be seen from fig. 27, the voltage required for the urea-containing two-electrode system is the lowest, indicating its good catalytic performance.
FIG. 28 is Co at a cell voltage of 1.5V 2 C/MoN-600/NF‖Co 2 Amperometric-time curve (i-t) diagram of C/MoN-600/NF (interpolated diagram) of urea electrolysis; as can be seen from fig. 28, it has good stability.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (9)
1. Rod-shaped Co 2 The preparation method of the C-MoN composite material is characterized by comprising the following steps of:
adding cobalt salt into water to obtain a first solution;
adding molybdate into water to obtain a second solution;
mixing the first solution and the second solution to obtain a mixed solution;
placing the foam nickel into the mixed solution, and reacting for 4-8 hours at 150-170 ℃ to obtain a precursor material;
respectively placing the precursor material and dicyandiamide in a tube furnace, heating to 500-700 ℃ under the protection of inert gas, and keeping for 1-3 h to obtain Co 2 C-MoN composite material.
2. A rod-shaped Co as claimed in claim 1 2 The preparation method of the C-MoN composite material is characterized in that the cobalt salt comprises at least one of cobalt sulfate, cobalt nitrate and cobalt chloride.
3. A rod-shaped Co as claimed in claim 1 2 The preparation method of the C-MoN composite material is characterized in that the molybdate comprises at least one of sodium molybdate, potassium molybdate and ammonium heptamolybdate.
4. A rod-shaped Co as claimed in claim 1 2 The preparation method of the C-MoN composite material is characterized in that in the step of adding cobalt salt into water, the molar volume ratio of the cobalt salt to the water is (0.5-2) mmol (15-25) mL;
and/or, in the step of adding molybdate to water, the molar volume ratio of molybdate to water is (0.1 to 0.2) mmol (5 to 15) mL;
and/or the molar mass ratio of cobalt salt to dicyandiamide is (0.5-2) mmol (0.3-0.7) g.
5. The method as claimed in claim 1Co rod 2 The preparation method of the C-MoN composite material is characterized in that a precursor material and dicyandiamide are respectively placed in a tube furnace, and under the protection of inert gas, the temperature is raised to 500-700 ℃ at the speed of 3-7 ℃/min and kept for 1-3 hours, thus obtaining Co 2 C-MoN composite material.
6. A rod-shaped Co as claimed in claim 1 2 The preparation method of the C-MoN composite material is characterized by further comprising the step of sequentially carrying out ultrasonic cleaning on the foam nickel by adopting hydrochloric acid, acetone, water and ethanol before the foam nickel is placed in the mixed solution.
7. A rod-shaped Co as claimed in claim 1 2 The preparation process of C-MoN composite material includes the steps of reaction of foamed nickel in mixed solution at 150-170 deg.c for 4-8 hr, washing and subsequent drying at 40-80 deg.c to obtain the precursor material.
8. Rod-shaped Co 2 The C-MoN composite material is characterized by being prepared by the preparation method according to any one of claims 1-7.
9. A rod-shaped Co as defined in claim 8 2 The application of the C-MoN composite material as a catalyst.
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