CN111155146A - Preparation method of vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material - Google Patents
Preparation method of vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material Download PDFInfo
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- CN111155146A CN111155146A CN201911367553.XA CN201911367553A CN111155146A CN 111155146 A CN111155146 A CN 111155146A CN 201911367553 A CN201911367553 A CN 201911367553A CN 111155146 A CN111155146 A CN 111155146A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 77
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 239000004201 L-cysteine Substances 0.000 claims abstract description 10
- 235000013878 L-cysteine Nutrition 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 150000002815 nickel Chemical class 0.000 claims abstract description 8
- 229910021550 Vanadium Chloride Inorganic materials 0.000 claims abstract description 5
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 claims abstract description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000012456 homogeneous solution Substances 0.000 abstract 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- 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—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
-
- 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
-
- 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 preparation method of a vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material, which comprises the following steps of: 1) grinding the graphene oxide and L-cysteine; 2) placing the mixture ground in the step 1) in a tubular furnace to prepare nitrogen-sulfur double-doped reduced graphene oxide; 3) preparing a nitrogen-sulfur double-doped reduced graphene oxide solution with the concentration of 0.5-1.0 mg/mL; 4) mixing urea and NH4F. Adding vanadium chloride and nickel salt into the nitrogen-sulfur double-doped reduced graphene oxide solution, and stirring until the solution is formedA homogeneous solution; 5) transferring the solution obtained in the step 4) into a reaction kettle to prepare a precursor NiV-LDH/NSG; 6) and putting the precursor NiV-LDH/NSG material and sodium hypophosphite into a tubular furnace, heating to 300-400 ℃, and preserving heat to obtain the vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material NiVP/NSG. The preparation method is low in cost and simple, and the obtained electrocatalytic material has good OER.
Description
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to a preparation method of a vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material.
Background
With the global energy crisis and the aggravation of environmental pollution, the development of clean and renewable energy has become a problem which is concerned and urgently needs to be solved. As a clean energy, the hydrogen has the characteristics of high energy density, high conversion efficiency, no pollution and the like, provides convenience for meeting the future huge energy demand, and has been widely researched at present. Electrocatalytic decomposition of water is an effective hydrogen production method, and the whole reaction process comprises two half reactions: oxygen Evolution Reactions (OER) and Hydrogen Evolution Reactions (HER). Because the oxygen evolution reaction is a four-electron process with slow kinetics, and the whole water decomposition process is limited by the kinetics of the oxygen evolution reaction, the development of the effective OER catalyst can reduce the energy barrier of the reaction and improve the water decomposition efficiency. Currently, Ir/Ru-based noble metal compounds are the most effective OER electrocatalysts. But their commercial use in the field of water electrolysis is severely limited due to their high cost, low content and poor stability. Therefore, there is a need to develop low cost alternative OER water electrolysis catalysts.
Researchers have developed a number of non-noble metal-based materials as OER catalysts, some of which are gradually coming into the field of people depending on the diversity of electrons in their 3D orbitals, such as transition metal (especially nickel-based) oxides and hydroxides, which can provide superior catalytic performance. More specifically, Layered Double Hydroxides (LDHs) have unique layered structure characteristics and excellent redox properties. NiV-LDH is a novel OER catalyst developed in recent years, and in an LDH material, NiV-LDH has good conductivity and easy electron transfer, and the intrinsic catalytic performance of the NiV-LDH on OER is proved in experiments and theoretical calculation. However, the OER activity needs to be further improved in practical applications. The nitrogen-sulfur double-doped reduced graphene oxide is a typical two-dimensional material, and nitrogen atoms and sulfur atoms are introduced into a graphene layer, so that better hydrophilicity and conductivity can be obtained compared with graphene oxide, the graphene oxide can be compounded with a layered double hydroxide material, and the conductivity of an electrocatalytic material is effectively increased; meanwhile, the stable two-dimensional layered structure of the nitrogen and sulfur reduced graphene oxide can provide a good supporting effect for the layered double hydroxide material, and the stability of the material structure is greatly improved.
Transition metal phosphides have great potential in electrocatalytic applications. Recent studies have shown that transition metal phosphides exhibit very high electrocatalytic activity in alkaline environments for oxygen evolution reactions. Meanwhile, the transition metal phosphide has the characteristics of rich content, low cost, good catalytic stability and the like, and has very important development potential in the field of water electrolysis.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a vanadium-doped nickel phosphide-composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material with better OER electrocatalytic performance.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material comprises the following steps:
1) grinding graphene oxide and L-cysteine, wherein the mass ratio of the graphene oxide to the L-cysteine is 1: 5-15;
2) placing the mixture ground in the step 1) in a tubular furnace, heating to 600-800 ℃ in an inert atmosphere, preserving heat for 1-4h, cooling to room temperature, and then washing and drying to obtain nitrogen-sulfur double-doped reduced graphene oxide;
3) dissolving nitrogen-sulfur double-doped reduced graphene oxide in deionized water, and performing ultrasonic treatment for 4-10h to obtain a uniformly mixed nitrogen-sulfur double-doped reduced graphene oxide solution with the concentration of 0.5-1.0 mg/mL;
4) mixing urea and NH4F. Vanadium and nickel chlorideAdding salt into the nitrogen-sulfur double-doped reduced graphene oxide solution, wherein urea and NH are added4The mass ratio of F is 1-4:1, the mass ratio of nickel salt to vanadium chloride is 3-9:1, urea and NH4F. The ratio of the total mass of the vanadium chloride and the nickel salt to the mass of the nitrogen-sulfur double-doped reduced graphene oxide is 22-50:1, and stirring is carried out until a uniform solution is formed;
5) transferring the solution in the step 4) into a reaction kettle, reacting for 8-18h at the temperature of 100-150 ℃, centrifuging to obtain a precipitate, washing the precipitate by using absolute ethyl alcohol, and drying at the temperature of 50-70 ℃ to obtain a precursor NiV-LDH/NSG;
6) putting the precursor NiV-LDH/NSG material obtained in the step 5) and sodium hypophosphite into a tubular furnace, heating the sample to 300-400 ℃ at the heating rate of 2-5 ℃/min in an inert atmosphere, preserving the heat for 1-5h, and cooling to room temperature to obtain the vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material NiVP/NSG.
Preferably, the graphene oxide in the step 1) is a single-layer graphene oxide.
Preferably, the grinding time in step 1) is 30 min.
Preferably, the inert atmosphere in the step 2) and the step 6) is nitrogen or argon.
Preferably, the nickel salt in the step 4) is nickel chloride or nickel nitrate.
The preparation method disclosed by the invention aims to design an OER catalyst which is low in cost, simple in method and good in performance, synthesize the LDH and nitrogen-sulfur double-doped reduced graphene oxide composite material, and carry out phosphorization on the material at the temperature of 300-400 ℃ to obtain the vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material. The material has large specific surface area and regular structure, and is an OER electro-catalytic material with excellent performance.
Drawings
FIG. 1 (a) (b) is a scanning electron micrograph of NiV-LDH/NSG prepared in example 1 of the present invention; (c) and (d) is a scanning electron microscope picture of the vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material after phosphorization in the embodiment 1.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Preparing nitrogen-sulfur double-doped reduced graphene oxide:
(a) placing 100mg of graphene oxide and 1.0g L-cysteine in a mortar for grinding for 30 min;
(b) and (c) placing the mixture obtained in the step (a) in a tubular furnace, heating to 600 ℃ in a nitrogen atmosphere, keeping the temperature for 2 hours, cooling to room temperature along with the furnace, washing and drying to obtain the nitrogen-sulfur double-doped reduced graphene oxide.
(2) Preparation of NiV-LDH/NSG:
(a) ultrasonically dispersing the obtained 30mg of nitrogen-sulfur double-doped reduced graphene oxide in 60mL of deionized water for 5h, and adding 0.900mmol of NiCl2、0.100mmol VCl310mmol of urea and 5mmol of NH4F, stirring the mixture until the mixture is uniformly mixed;
(b) transferring the solution in the step (a) into a reaction kettle, then reacting for 16h at 120 ℃, centrifuging to obtain a precipitate, washing the precipitate by using absolute ethyl alcohol, and drying at 60 ℃ to obtain a precursor material NiV-LDH/NSG;
(3) preparation of NiVP/NSG material:
and (3) placing the NiV-LDH/NSG material obtained in the step (2) into a tube furnace, heating to 350 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, preserving the temperature for 1h, and then cooling to room temperature to obtain the vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material.
FIG. 1 (a) (b) is a scanning electron micrograph of NiV-LDH/NSG prepared in example 1 of the present invention, from which it can be clearly understood thatClearly showing the microstructure and the size of the material, the surface of the nitrogen-sulfur double-doped reduced graphene oxide is covered with a layer of uniform flaky structure; (c) and (d) is an SEM picture of the phosphated vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material in example 1, and compared with (a) and (b), the morphology of the nanosheet has no obvious change in the phosphating process, so that the nanosheet is well retained. In 1mol/L KOH electrolyte, the current density is 10mA/cm-2Its overpotential is only 300 mV.
Example 2
(1) Preparing nitrogen-sulfur double-doped reduced graphene oxide:
(a) placing 100mg of graphene oxide and 0.5g L-cysteine in a mortar for grinding for 30 min;
(b) and (c) placing the mixture obtained in the step (a) in a tubular furnace, heating to 700 ℃ in a nitrogen atmosphere, keeping the temperature for 1h, cooling to room temperature along with the furnace, washing and drying to obtain the nitrogen-sulfur double-doped reduced graphene oxide.
(2) Preparation of NiV-LDH/NSG:
(a) ultrasonically dispersing the obtained 30mg of nitrogen-sulfur double-doped reduced graphene oxide in 40mL of deionized water for 5h, and adding 0.833mmol of NiCl2、0.166mmol VCl310mmol of urea and 5mmol of NH4F, stirring the mixture until the mixture is uniformly mixed;
(b) transferring the solution in the step (a) into a reaction kettle, then reacting for 16h at 120 ℃, centrifuging to obtain a precipitate, washing the precipitate by using absolute ethyl alcohol, and drying at 60 ℃ to obtain a precursor material NiV-LDH/NSG;
(3) preparation of NiVP/NSG material:
and (3) placing the NiV-LDH/NSG material obtained in the step (2) into a tube furnace, heating to 350 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, preserving the temperature for 1h, and then cooling to room temperature to obtain the vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material.
In 1mol/L KOH electrolyte, the current density is 10mA/cm-2Its overpotential is only 313 mV.
Example 3
(1) Preparing nitrogen-sulfur double-doped reduced graphene oxide:
(a) placing 100mg of graphene oxide and 1.5g L-cysteine in a mortar for grinding for 30 min;
(b) and (c) placing the mixture obtained in the step (a) in a tubular furnace, heating to 800 ℃ in a nitrogen atmosphere, keeping the temperature for 4 hours, cooling to room temperature along with the furnace, washing and drying to obtain the nitrogen-sulfur double-doped reduced graphene oxide.
(2) Preparation of NiV-LDH/NSG:
(a) ultrasonically dispersing the obtained 30mg of nitrogen-sulfur double-doped reduced graphene oxide in 30mL of deionized water for 5h, and adding 0.750mmol of NiCl2、0.250mmol VCl310mmol of urea and 5mmol of NH4F, stirring the mixture until the mixture is uniformly mixed;
(b) transferring the solution in the step (a) into a reaction kettle, then reacting for 16h at 120 ℃, centrifuging to obtain a precipitate, washing the precipitate by using absolute ethyl alcohol, and drying at 60 ℃ to obtain a precursor material NiV-LDH/NSG;
(3) preparation of NiVP/NSG material:
and (3) placing the NiV-LDH/NSG material obtained in the step (2) into a tube furnace, heating to 350 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, preserving the temperature for 1h, and then cooling to room temperature to obtain the vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material.
In 1mol/L KOH electrolyte, the current density is 10mA/cm-2Its overpotential is only 325 mV.
Example 4
(1) Preparing nitrogen-sulfur double-doped reduced graphene oxide:
(a) placing 100mg of graphene oxide and 1.5g L-cysteine in a mortar for grinding for 30 min;
(b) and (c) placing the mixture obtained in the step (a) in a tubular furnace, heating to 800 ℃ in a nitrogen atmosphere, keeping the temperature for 4 hours, cooling to room temperature along with the furnace, washing and drying to obtain the nitrogen-sulfur double-doped reduced graphene oxide.
(2) Preparation of NiV-LDH/NSG:
(a) dispersing the obtained 30mg of nitrogen-sulfur double-doped reduced graphene oxide in 30mL of deionized water for 4h by ultrasonic treatment, and adding0.750mmol of Ni (NO)3)2、0.250mmol VCl35mmol of urea and 5mmol of NH4F, stirring the mixture until the mixture is uniformly mixed;
(b) transferring the solution in the step (a) into a reaction kettle, then reacting for 8h at 100 ℃, centrifuging to obtain a precipitate, washing the precipitate with absolute ethyl alcohol, and drying at 50 ℃ to obtain a precursor material NiV-LDH/NSG;
(3) preparation of NiVP/NSG material:
and (3) placing the NiV-LDH/NSG material obtained in the step (2) into a tube furnace, heating to 300 ℃ at the speed of 3 ℃/min in the nitrogen atmosphere, preserving the temperature for 1h, and then cooling to room temperature to obtain the vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material.
Example 5
(1) Preparing nitrogen-sulfur double-doped reduced graphene oxide:
(a) placing 100mg of graphene oxide and 1.0g L-cysteine in a mortar for grinding for 30 min;
(b) and (c) placing the mixture obtained in the step (a) in a tubular furnace, heating to 600 ℃ in a nitrogen atmosphere, keeping the temperature for 2 hours, cooling to room temperature along with the furnace, washing and drying to obtain the nitrogen-sulfur double-doped reduced graphene oxide.
(2) Preparation of NiV-LDH/NSG:
(a) ultrasonically dispersing the obtained 30mg of nitrogen-sulfur double-doped reduced graphene oxide in 60mL of deionized water for 7h, and adding 0.900mmol of NiCl2、0.100mmol VCl320mmol of urea and 5mmol of NH4F, stirring the mixture until the mixture is uniformly mixed;
(b) transferring the solution in the step (a) into a reaction kettle, then reacting for 18h at 150 ℃, centrifuging to obtain a precipitate, washing the precipitate with absolute ethyl alcohol, and drying at 70 ℃ to obtain a precursor material NiV-LDH/NSG;
(3) preparation of NiVP/NSG material:
and (3) placing the NiV-LDH/NSG material obtained in the step (2) into a tube furnace, heating to 400 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, preserving the temperature for 2h, and then cooling to room temperature to obtain the vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material.
Example 6
(1) Preparing nitrogen-sulfur double-doped reduced graphene oxide:
(a) placing 100mg of graphene oxide and 1.5g L-cysteine in a mortar for grinding for 30 min;
(b) and (c) placing the mixture obtained in the step (a) in a tubular furnace, heating to 700 ℃ in a nitrogen atmosphere, keeping the temperature for 4 hours, cooling to room temperature along with the furnace, washing and drying to obtain the nitrogen-sulfur double-doped reduced graphene oxide.
(2) Preparation of NiV-LDH/NSG:
(a) ultrasonically dispersing the obtained 30mg of nitrogen-sulfur double-doped reduced graphene oxide in 60mL of deionized water for 10h, and adding 0.900mmol of NiCl2、0.100mmol VCl310mmol of urea and 5mmol of NH4F, stirring the mixture until the mixture is uniformly mixed;
(b) transferring the solution in the step (a) into a reaction kettle, then reacting for 18h at 100 ℃, centrifuging to obtain a precipitate, washing the precipitate by using absolute ethyl alcohol, and drying at 70 ℃ to obtain a precursor material NiV-LDH/NSG;
(3) preparation of NiVP/NSG material:
putting the NiV-LDH/NSG material obtained in the step (2) into a tube furnace, heating to 300 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, preserving the temperature for 5h, and then cooling to room temperature to obtain the vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material
Example 7
(1) Preparing nitrogen-sulfur double-doped reduced graphene oxide:
(a) placing 100mg of graphene oxide and 1.0g L-cysteine in a mortar for grinding for 30 min;
(b) and (c) placing the mixture obtained in the step (a) in a tubular furnace, heating to 700 ℃ in a nitrogen atmosphere, keeping the temperature for 4 hours, cooling to room temperature along with the furnace, washing and drying to obtain the nitrogen-sulfur double-doped reduced graphene oxide.
(2) Preparation of NiV-LDH/NSG:
(a) dispersing the obtained 30mg of nitrogen-sulfur double-doped reduced graphene oxide in 60mL of deionized water for 4h by ultrasonic treatment, and adding 0.900mmol of Ni (NO)3)2、0.100mmol VCl310mmol of urea and 5mmol of NH4F, stirring the mixture until the mixture is uniformly mixed;
(b) transferring the solution in the step (a) into a reaction kettle, then reacting for 16h at 100 ℃, centrifuging to obtain a precipitate, washing the precipitate by using absolute ethyl alcohol, and drying at 70 ℃ to obtain a precursor material NiV-LDH/NSG;
(3) preparation of NiVP/NSG material:
and (3) placing the NiV-LDH/NSG material obtained in the step (2) into a tube furnace, heating to 300 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, preserving the temperature for 5 hours, and then cooling to room temperature to obtain the vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material.
The foregoing detailed description is intended to illustrate and not limit the invention, which is intended to be within the spirit and scope of the appended claims, and any changes and modifications that fall within the true spirit and scope of the invention are intended to be covered by the following claims.
Claims (5)
1. A preparation method of a vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material is characterized by comprising the following steps of:
1) grinding graphene oxide and L-cysteine, wherein the mass ratio of the graphene oxide to the L-cysteine is 1: 5-15;
2) placing the mixture ground in the step 1) in a tubular furnace, heating to 600-800 ℃ in an inert atmosphere, preserving heat for 1-4h, cooling to room temperature, and then washing and drying to obtain nitrogen-sulfur double-doped reduced graphene oxide;
3) dissolving nitrogen-sulfur double-doped reduced graphene oxide in deionized water, and performing ultrasonic treatment for 4-10h to obtain a uniformly mixed nitrogen-sulfur double-doped reduced graphene oxide solution with the concentration of 0.5-1.0 mg/mL;
4) mixing urea and NH4F. Adding vanadium chloride and nickel salt into the nitrogen-sulfur double-doped reduced graphene oxide solution, wherein urea and NH are added4The mass ratio of F is 1-4:1, the mass ratio of nickel salt to vanadium chloride is 3-9:1, urea and NH4F. Chlorination ofThe ratio of the total mass of the four substances of vanadium and nickel salt to the mass of the nitrogen-sulfur double-doped reduced graphene oxide is 22-50:1, and stirring is carried out until a uniform solution is formed;
5) transferring the solution in the step 4) into a reaction kettle, reacting for 8-18h at the temperature of 100-150 ℃, centrifuging to obtain a precipitate, washing the precipitate by using absolute ethyl alcohol, and drying at the temperature of 50-70 ℃ to obtain a precursor NiV-LDH/NSG;
6) putting the precursor NiV-LDH/NSG material obtained in the step 5) and sodium hypophosphite into a tubular furnace, heating the sample to 300-400 ℃ at the heating rate of 2-5 ℃/min in an inert atmosphere, preserving the heat for 1-5h, and cooling to room temperature to obtain the vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material NiVP/NSG.
2. The method of claim 1, wherein: the graphene oxide in the step 1) is single-layer graphene oxide.
3. The method of claim 1, wherein: the grinding time in the step 1) is 30 min.
4. The method of claim 1, wherein: the inert gas in the steps 2) and 6) is nitrogen or argon.
5. The method of claim 1, wherein: the nickel salt in the step 4) is nickel chloride or nickel nitrate.
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