CN111068726A - Preparation method of iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material - Google Patents
Preparation method of iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material Download PDFInfo
- Publication number
- CN111068726A CN111068726A CN201911173612.XA CN201911173612A CN111068726A CN 111068726 A CN111068726 A CN 111068726A CN 201911173612 A CN201911173612 A CN 201911173612A CN 111068726 A CN111068726 A CN 111068726A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- nitrogen
- doped
- reduced graphene
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 95
- 239000000463 material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 238000001816 cooling Methods 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 25
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 25
- 239000002244 precipitate Substances 0.000 claims abstract description 25
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 23
- 239000012298 atmosphere Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 15
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001704 evaporation Methods 0.000 claims abstract description 13
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims abstract description 5
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 17
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 10
- 229910052603 melanterite Inorganic materials 0.000 description 10
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
-
- 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 preparation method of an iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material, which comprises the following steps: 1) dissolving graphene oxide, performing ultrasonic treatment to obtain a uniform graphene oxide solution, adding melamine, stirring, and evaporating to obtain a light black solid; 2) putting the light black solid into a tube furnace, heating and preserving heat in an inert atmosphere, cooling to room temperature, washing and drying to obtain nitrogen-doped reduced graphene oxide; 3) dissolving nitrogen-doped reduced graphene oxide in deionized water to obtain a nitrogen-doped reduced graphene oxide solution; 4) mixing urea and NH4F. Adding nickel chloride hexahydrate and ferrous sulfate heptahydrate into the nitrogen-doped reduced graphene oxide solution, and stirringHomogenizing; 5) transferring the solution to a reaction kettle, centrifuging after reaction to obtain dark green precipitate, washing and drying to obtain a precursor material; 6) and heating the precursor material in an inert atmosphere, preserving heat, and cooling to room temperature to obtain the material. The preparation method is simple, low in cost and excellent in catalytic performance.
Description
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to a preparation method of an iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material.
Background
With the progress and development of society, the demand of materials and energy sources is more and more abundant, and the consumption of fossil energy (coal, oil and natural gas) is increasing. As an irreproducible resource, fossil energy reserves are limited, and exhaustion thereof is inevitable. In addition, the fossil energy can generate a large amount of harmful substances and carbon dioxide in the using process, and brings about very adverse effects on the global climate and environment. Therefore, the production of clean, renewable and other environment-friendly energy sources is concerned and needs to be solved urgently. Hydrogen is considered to be an excellent alternative energy source to replace conventional fossil fuels due to its high energy density and good renewable property. At present, hydrogen production by electrolyzing water is a hydrogen production technical means with wide application. Electrocatalytic water decomposition mainly consists of two half reactions, an Oxygen Evolution Reaction (OER) and a Hydrogen Evolution Reaction (HER), but since OER is a slow kinetic four electron, the overall efficiency of the electrochemical water decomposition is severely limited. To date, Ir/Ru-based metal oxides have been recognized as excellent OER catalysts due to their good electron transfer kinetics and electrocatalytic activity. However, their high cost and scarcity greatly limit their commercial application. Therefore, designing inexpensive, stable, alternative non-noble metal catalysts remains a pressing need and challenge.
Layered Double Hydroxides (LDHs) have become very promising non-noble metal electrocatalysts in alkaline electrolyte solutions due to their special two-dimensional structure, large surface area, adjustable composition and rich content. Recent studies have shown that NiFe-LDH has broad prospects as a water-decomposition electrocatalyst due to the strong synergistic effect between Ni and Fe ions. Nevertheless, its electrocatalytic water splitting performance is still limited by its low conductivity and slower water dissociation process. To increase the electrocatalytic efficiency of LDHs, electronic structure modulation and hybridization may be used to accelerate charge transfer and optimize the binding energy between the catalyst and reaction intermediates by nano-structuring to increase the active surface area. The nitrogen-doped reduced graphene oxide is a typical two-dimensional material and has better conductivity. The conductivity of the electrocatalytic material is effectively increased by compounding the nitrogen-doped reduced graphene oxide with the layered double hydroxide; meanwhile, the stable structure of the nitrogen-doped reduced graphene oxide provides a good supporting effect of the layered double hydroxide, and the stability of the structure is improved.
The transition metal phosphide has low manufacturing cost, good electrochemical stability, controllable central metal valence and proper bond energy to an OER intermediate, so that the transition metal phosphide becomes a novel catalyst for electrochemical water decomposition of non-noble metals. From the results of the present research, in order to further improve the electrochemical performance, it is mainly possible to optimize the electronic structure and the surface potential of the catalyst by doping one or more metal atoms, extending from monometallic phosphides to multimetal phosphides, thus obtaining a highly active catalyst capable of reducing the overpotential and enhancing the exchange current.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of an iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material with good OER electrocatalytic performance.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of an iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material comprises the following steps:
1) dissolving graphene oxide in deionized water, performing ultrasonic treatment to obtain a uniform graphene oxide solution, adding melamine, wherein the mass ratio of the graphene oxide to the melamine is 1:5-10, and stirring and evaporating to obtain a light black solid;
2) putting the light black solid prepared in the step 1) into a tube furnace, heating to 700-900 ℃ in an inert atmosphere, preserving heat for 1-3h, cooling to room temperature, washing and drying to obtain nitrogen-doped reduced graphene oxide;
3) dissolving nitrogen-doped reduced graphene oxide in deionized water, and performing ultrasonic treatment for 3-7h to obtain a uniformly mixed nitrogen-doped reduced graphene oxide solution with the concentration of 0.75-1 mg/mL;
4) mixing urea and NH4F. Adding nickel chloride hexahydrate and ferrous sulfate heptahydrate into the nitrogen-doped reduced graphene oxide solution, wherein the mass ratio of the nickel chloride hexahydrate to the ferrous sulfate heptahydrate is 2-8:1, and adding urea and NH4The mass ratio of the F is 1-3:1, 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 6-10h at the temperature of 100-130 ℃, centrifuging to obtain dark green precipitates, washing the precipitates with absolute ethyl alcohol, and drying at the temperature of 50-70 ℃ to obtain a precursor material NiFe-LDH/NG;
6) placing the precursor material obtained in the step 5) in a tubular furnace, heating the sample to 300-360 ℃ at the heating rate of 1-5 ℃/min in an inert atmosphere, preserving the temperature for 1-4h, and cooling to room temperature to obtain the iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material NiFeP/NG.
Preferably, the graphene oxide in the step 1) is a single-layer graphene oxide.
Preferably, the inert atmosphere in the steps 2) and 6) is one of nitrogen and argon.
The preparation method disclosed by the invention aims to design a catalyst which is simple in preparation method, low in cost and excellent in OER catalytic performance, firstly synthesizes the LDH and nitrogen-doped reduced graphene oxide composite nanomaterial, and performs phosphating treatment on the material at the temperature of 300-. The material has the characteristics of large specific surface area, regular appearance, uniform doping and the like, and is an excellent electro-catalytic material.
Drawings
FIG. 1 (a) (b) is a scanning electron microscope image of NiFe-LDH/NG prepared in example 1 of the present invention; (c) and (d) is a scanning electron microscope picture of the iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material after phosphorization in the embodiment 1.
Fig. 2 is an XRD chart of the iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material in example 1 of the present invention.
Fig. 3 is an LSV curve and a Tafel slope curve of OER of the iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material after phosphorization in example 1 of the present invention.
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) Preparation of nitrogen-doped reduced graphene oxide
(a) Dissolving 300mg of graphene oxide in 300mL of deionized water, carrying out ultrasonic treatment for 5 hours, adding 1.5g of melamine, and stirring and evaporating to obtain a light black solid;
(b) and (c) placing the light black solid obtained in the step (a) in a tubular furnace, heating to 800 ℃ in an inert atmosphere, keeping the temperature for 1h, cooling to room temperature along with the furnace, washing and drying to obtain the nitrogen-doped reduced graphene oxide.
(2) Preparation of NiFe-LDH/NG:
(a) dispersing the obtained 30mg of nitrogen-doped reduced graphene oxide in 35mL of deionized water by ultrasonic treatment for 5h, and adding 0.833mmol of NiCl2·6H2O、0.166mmol FeSO4·7H2O, 10mmol Urea and 5mmol NH4F, stirring the mixture until the mixture is uniformly mixed;
(b) transferring the solution in the step (a) to a reaction kettle, then reacting for 8h at 120 ℃, centrifuging to obtain dark green precipitate, washing the precipitate with absolute ethyl alcohol, and drying at 60 ℃ to obtain a precursor material NiFe-LDH/NG;
(3) preparation of NiFeP/NG material:
and (3) placing the NiFe-LDH/NG material obtained in the step (2) into a tube furnace, heating to 320 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, preserving the temperature for 2h, and then cooling to room temperature to obtain the iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material.
FIG. 1 (a) (b) is a scanning electron microscope picture of NiFe-LDH/NG prepared in example 1 of the present invention, from which it can be clearly seen that the microscopic size of the material is, and the surface of the nitrogen-doped reduced graphene oxide is covered with a layer of uniform scale-like structure; (c) and (d) is a scanning electron microscope picture of the iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material after phosphorization in the embodiment 1, and it can be seen from the picture that the morphology of the LDH nanosheet is well preserved in the phosphorization process. FIG. 3 is a diagram of the electrochemical performance of an iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material, and it can be seen from the diagram that the composite material has a good OER performance, and the current density is 10mA/cm in a KOH electrolyte of 1mol/L-2When the voltage is higher than the threshold voltage, the overpotential is only 268mV, and the slope of the Tafel curve is 72mV dec-1。
Example 2
(1) Preparation of nitrogen-doped reduced graphene oxide
(a) Dissolving 300mg of graphene oxide in 300mL of deionized water, carrying out ultrasonic treatment for 5 hours, adding 1.5g of melamine, and stirring and evaporating to obtain a light black solid;
(b) and (c) placing the light black solid obtained in the step (a) in a tubular furnace, heating to 800 ℃ in an inert atmosphere, keeping the temperature for 1h, cooling to room temperature along with the furnace, washing and drying to obtain the nitrogen-doped reduced graphene oxide.
(2) Preparation of NiFe-LDH/NG:
(a) dispersing the obtained 30mg of nitrogen-doped reduced graphene oxide in 35mL of deionized water for 5h by ultrasonic treatment, and adding 0.667mmol NiCl2·6H2O、0.333mmol FeSO4·7H2O, 10mmol urea and 5mmol NH4F are stirred to a uniformly mixed solution;
(b) transferring the solution in the step (a) to a reaction kettle, then reacting for 8h at 120 ℃, centrifuging to obtain dark green precipitate, washing the precipitate with absolute ethyl alcohol, and drying at 60 ℃ to obtain a precursor material NiFe-LDH/NG;
(3) preparation of NiFeP/NG material:
and (3) placing the NiFe-LDH/NG material obtained in the step (2) into a tube furnace, heating to 320 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, preserving the temperature for 2h, and then cooling to room temperature to obtain the iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material.
In 1mol/L KOH electrolyte, the current density is 10mA/cm-2Its overpotential is only 330 mV.
Example 3
(1) Preparation of nitrogen-doped reduced graphene oxide
(a) Dissolving 300mg of graphene oxide in 300mL of deionized water, carrying out ultrasonic treatment for 5 hours, adding 1.5g of melamine, and stirring and evaporating to obtain a light black solid;
(b) and (c) placing the light black solid obtained in the step (a) in a tubular furnace, heating to 800 ℃ in an inert atmosphere, keeping the temperature for 1h, cooling to room temperature along with the furnace, washing and drying to obtain the nitrogen-doped reduced graphene oxide.
(2) Preparation of NiFe-LDH/NG:
(a) dispersing the obtained 30mg of nitrogen-doped reduced graphene oxide in 35mL of deionized water for 5h by ultrasonic treatment, and adding 0.889mmol of NiCl2·6H2O、0.111mmol FeSO4·7H2O, 10mmol urea and 5mmol NH4F are stirred to a uniformly mixed solution;
(b) transferring the solution in the step (a) to a reaction kettle, then reacting for 8h at 120 ℃, centrifuging to obtain dark green precipitate, washing the precipitate with absolute ethyl alcohol, and drying at 60 ℃ to obtain a precursor material NiFe-LDH/NG;
(3) preparation of NiFeP/NG material:
and (3) placing the NiFe-LDH/NG material obtained in the step (2) into a tube furnace, heating to 320 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, preserving the temperature for 2h, and then cooling to room temperature to obtain the iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material.
In 1mol/L KOH electrolyte, the current density is 10mA/cm-2Its overpotential is only 310 mV.
Example 4
(1) Preparation of nitrogen-doped reduced graphene oxide
(a) Dissolving 300mg of graphene oxide in 300mL of deionized water, carrying out ultrasonic treatment for 5 hours, adding 1.5g of melamine, and stirring and evaporating to obtain a light black solid;
(b) and (c) placing the light black solid obtained in the step (a) in a tubular furnace, heating to 800 ℃ in an inert atmosphere, keeping the temperature for 1h, cooling to room temperature along with the furnace, washing and drying to obtain the nitrogen-doped reduced graphene oxide.
(2) Preparation of NiFe-LDH/NG:
(a) dispersing the obtained 30mg of nitrogen-doped reduced graphene oxide in 40mL of deionized water by ultrasonic treatment for 5h, and adding 0.833mmol of NiCl2·6H2O、0.166mmol FeSO4·7H2O, 10mmol urea and 5mmol NH4F are stirred to a uniformly mixed solution;
(b) transferring the solution in the step (a) to a reaction kettle, then reacting for 6h at 100 ℃, centrifuging to obtain dark green precipitate, washing the precipitate with absolute ethyl alcohol, and drying at 60 ℃ to obtain a precursor material NiFe-LDH/NG;
(3) preparation of NiFeP/NG material:
and (3) placing the NiFe-LDH/NG material obtained in the step (2) into a tube furnace, heating to 320 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, preserving the temperature for 2h, and then cooling to room temperature to obtain the iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material.
In 1mol/L KOH electrolyte, the current density is 10mA/cm-2Its overpotential is only 324 mV.
Example 5
(1) Preparation of nitrogen-doped reduced graphene oxide
(a) Dissolving 300mg of graphene oxide in 300mL of deionized water, carrying out ultrasonic treatment for 5 hours, adding 3.0g of melamine, and stirring and evaporating to obtain a light black solid;
(b) and (c) placing the light black solid obtained in the step (a) in a tubular furnace, heating to 800 ℃ in an inert atmosphere, keeping the temperature for 1h, cooling to room temperature along with the furnace, washing and drying to obtain the nitrogen-doped reduced graphene oxide.
(2) Preparation of NiFe-LDH/NG:
(a) dispersing the obtained 30mg of nitrogen-doped reduced graphene oxide in 30mL of deionized water by ultrasonic wave for 5h, and adding 0.667mmol NiCl2·6H2O、0.333mmol FeSO4·7H2O, 10mmol urea and 5mmol NH4F are stirred to a uniformly mixed solution;
(b) transferring the solution in the step (a) to a reaction kettle, then reacting for 10h at 130 ℃, centrifuging to obtain dark green precipitate, washing the precipitate with absolute ethyl alcohol, and drying at 60 ℃ to obtain a precursor material NiFe-LDH/NG;
(3) preparation of NiFeP/NG material:
and (3) placing the NiFe-LDH/NG material obtained in the step (2) into a tube furnace, heating to 320 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, preserving the temperature for 2h, and then cooling to room temperature to obtain the iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material.
Example 6
(1) Preparation of nitrogen-doped reduced graphene oxide
(a) Dissolving 300mg of graphene oxide in 300mL of deionized water, carrying out ultrasonic treatment for 5 hours, adding 1.5g of melamine, and stirring and evaporating to obtain a light black solid;
(b) and (c) placing the light black solid obtained in the step (a) in a tubular furnace, heating to 700 ℃ in an inert atmosphere, keeping the temperature for 1h, cooling to room temperature along with the furnace, washing and drying to obtain the nitrogen-doped reduced graphene oxide.
(2) Preparation of NiFe-LDH/NG:
(a) dispersing the obtained 30mg of nitrogen-doped reduced graphene oxide in 35mL of deionized water for 5h by ultrasonic treatment, and adding 0.667mmol NiCl2·6H2O、0.333mmol FeSO4·7H2O, 10mmol urea and 5mmol NH4F are stirred to a uniformly mixed solution;
(b) transferring the solution in the step (a) to a reaction kettle, then reacting for 8h at 120 ℃, centrifuging to obtain dark green precipitate, washing the precipitate with absolute ethyl alcohol, and drying at 60 ℃ to obtain a precursor material NiFe-LDH/NG;
(3) preparation of NiFeP/NG material:
and (3) placing the NiFe-LDH/NG material obtained in the step (2) into a tube furnace, heating to 300 ℃ at the speed of 1 ℃/min in the nitrogen atmosphere, preserving the temperature for 1h, and then cooling to room temperature to obtain the iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material.
Example 7
(1) Preparation of nitrogen-doped reduced graphene oxide
(a) Dissolving 300mg of graphene oxide in 300mL of deionized water, carrying out ultrasonic treatment for 5 hours, adding 2.4g of melamine, and stirring and evaporating to obtain a light black solid;
(b) and (c) placing the light black solid obtained in the step (a) in a tubular furnace, heating to 900 ℃ in an inert atmosphere, keeping the temperature for 2 hours, cooling to room temperature along with the furnace, washing and drying to obtain the nitrogen-doped reduced graphene oxide.
(2) Preparation of NiFe-LDH/NG:
(a) dispersing the obtained 30mg of nitrogen-doped reduced graphene oxide in 35mL of deionized water for 5h by ultrasonic treatment, and adding 0.667mmol NiCl2·6H2O、0.333mmol FeSO4·7H2O, 10mmol urea and 5mmol NH4F are stirred to a uniformly mixed solution;
(b) transferring the solution in the step (a) to a reaction kettle, then reacting for 8h at 120 ℃, centrifuging to obtain dark green precipitate, washing the precipitate with absolute ethyl alcohol, and drying at 60 ℃ to obtain a precursor material NiFe-LDH/NG;
(3) preparation of NiFeP/NG material:
and (3) placing the NiFe-LDH/NG material obtained in the step (2) into a tube furnace, heating to 340 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, preserving the heat for 4h, and then cooling to room temperature to obtain the iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material.
Example 8
(1) Preparation of nitrogen-doped reduced graphene oxide
(a) Dissolving 300mg of graphene oxide in 300mL of deionized water, carrying out ultrasonic treatment for 5 hours, adding 1.5g of melamine, and stirring and evaporating to obtain a light black solid;
(b) and (c) placing the light black solid obtained in the step (a) in a tubular furnace, heating to 800 ℃ in an inert atmosphere, keeping the temperature for 3 hours, cooling to room temperature along with the furnace, washing and drying to obtain the nitrogen-doped reduced graphene oxide.
(2) Preparation of NiFe-LDH/NG:
(a) dispersing the obtained 30mg of nitrogen-doped reduced graphene oxide in 35mL of deionized water for 3h by ultrasonic, and adding 0.667mmol NiCl2·6H2O、0.333mmol FeSO4·7H2O, 10mmol urea and 5mmol NH4F are stirred to a uniformly mixed solution;
(b) transferring the solution in the step (a) to a reaction kettle, then reacting for 8h at 120 ℃, centrifuging to obtain dark green precipitate, washing the precipitate with absolute ethyl alcohol, and drying at 60 ℃ to obtain a precursor material NiFe-LDH/NG;
(3) preparation of NiFeP/NG material:
and (3) placing the NiFe-LDH/NG material obtained in the step (2) into a tube furnace, heating to 360 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, preserving the temperature for 2h, and then cooling to room temperature to obtain the iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material.
Example 9
(1) Preparation of nitrogen-doped reduced graphene oxide
(a) Dissolving 300mg of graphene oxide in 300mL of deionized water, carrying out ultrasonic treatment for 5 hours, adding 1.5g of melamine, and stirring and evaporating to obtain a light black solid;
(b) and (c) placing the light black solid obtained in the step (a) in a tubular furnace, heating to 800 ℃ in an inert atmosphere, keeping the temperature for 3 hours, cooling to room temperature along with the furnace, washing and drying to obtain the nitrogen-doped reduced graphene oxide.
(2) Preparation of NiFe-LDH/NG:
(a) dispersing the obtained 30mg of nitrogen-doped reduced graphene oxide in 35mL of deionized water for 7h by ultrasonic treatment, and adding 0.667mmol NiCl2·6H2O、0.333mmol FeSO4·7H2O, 5mmol urea and 5mmol NH4F are stirred to a uniformly mixed solution;
(b) transferring the solution in the step (a) to a reaction kettle, then reacting for 8h at 120 ℃, centrifuging to obtain dark green precipitate, washing the precipitate with absolute ethyl alcohol, and drying at 50 ℃ to obtain a precursor material NiFe-LDH/NG;
(3) preparation of NiFeP/NG material:
and (3) placing the NiFe-LDH/NG material obtained in the step (2) into a tube furnace, heating to 360 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, preserving the temperature for 2h, and then cooling to room temperature to obtain the iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material.
Example 10
(1) Preparation of nitrogen-doped reduced graphene oxide
(a) Dissolving 300mg of graphene oxide in 300mL of deionized water, carrying out ultrasonic treatment for 5 hours, adding 1.5g of melamine, and stirring and evaporating to obtain a light black solid;
(b) and (c) placing the light black solid obtained in the step (a) in a tubular furnace, heating to 800 ℃ in an inert atmosphere, keeping the temperature for 3 hours, cooling to room temperature along with the furnace, washing and drying to obtain the nitrogen-doped reduced graphene oxide.
(2) Preparation of NiFe-LDH/NG:
(a) dispersing the obtained 30mg of nitrogen-doped reduced graphene oxide in 35mL of deionized water for 5h by ultrasonic treatment, and adding 0.667mmol NiCl2·6H2O、0.333mmol FeSO4·7H2O, 15mmol urea and 5mmol NH4F are stirred to a uniformly mixed solution;
(b) transferring the solution in the step (a) to a reaction kettle, then reacting for 8h at 120 ℃, centrifuging to obtain dark green precipitate, washing the precipitate with absolute ethyl alcohol, and drying at 70 ℃ to obtain a precursor material NiFe-LDH/NG;
(3) preparation of NiFeP/NG material:
and (3) placing the NiFe-LDH/NG material obtained in the step (2) into a tube furnace, heating to 360 ℃ at the speed of 2 ℃/min in the nitrogen atmosphere, preserving the temperature for 2h, and then cooling to room temperature to obtain the iron-doped nickel phosphide composite nitrogen-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 (3)
1. A preparation method of an iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material is characterized by comprising the following steps of:
1) dissolving graphene oxide in deionized water, performing ultrasonic treatment to obtain a uniform graphene oxide solution, adding melamine, wherein the mass ratio of the graphene oxide to the melamine is 1:5-10, and stirring and evaporating to obtain a light black solid;
2) putting the light black solid prepared in the step 1) into a tube furnace, heating to 700-900 ℃ in an inert atmosphere, preserving heat for 1-3h, cooling to room temperature, washing and drying to obtain nitrogen-doped reduced graphene oxide;
3) dissolving nitrogen-doped reduced graphene oxide in deionized water, and performing ultrasonic treatment for 3-7h to obtain a uniformly mixed nitrogen-doped reduced graphene oxide solution with the concentration of 0.75-1 mg/mL;
4) mixing urea and NH4F. Adding nickel chloride hexahydrate and ferrous sulfate heptahydrate into the nitrogen-doped reduced graphene oxide solution, wherein the mass ratio of the nickel chloride hexahydrate to the ferrous sulfate heptahydrate is 2-8:1, and adding urea and NH4The mass ratio of the F is 1-3:1, 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 6-10h at the temperature of 100-130 ℃, centrifuging to obtain dark green precipitates, washing the precipitates with absolute ethyl alcohol, and drying at the temperature of 50-70 ℃ to obtain a precursor material NiFe-LDH/NG;
6) placing the precursor material obtained in the step 5) in a tubular furnace, heating the sample to 300-360 ℃ at the heating rate of 1-5 ℃/min in an inert atmosphere, preserving the temperature for 1-4h, and cooling to room temperature to obtain the iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material NiFeP/NG.
2. The preparation method of the iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material as claimed in claim 1, wherein the preparation method comprises the following steps: the graphene oxide in the step 1) is single-layer graphene oxide.
3. The preparation method of the iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material as claimed in claim 1, wherein the preparation method comprises the following steps: the inert atmosphere in the steps 2) and 6) is one of nitrogen and argon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911173612.XA CN111068726A (en) | 2019-11-26 | 2019-11-26 | Preparation method of iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911173612.XA CN111068726A (en) | 2019-11-26 | 2019-11-26 | Preparation method of iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111068726A true CN111068726A (en) | 2020-04-28 |
Family
ID=70311699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911173612.XA Pending CN111068726A (en) | 2019-11-26 | 2019-11-26 | Preparation method of iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111068726A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113769759A (en) * | 2021-09-23 | 2021-12-10 | 深圳市康弘环保技术有限公司 | Room-temperature catalytic formaldehyde oxidation composite material, preparation method thereof and air purifier |
| CN114229969A (en) * | 2021-12-30 | 2022-03-25 | 山西诺沃科技有限公司 | Electronic control ionic membrane material for separating phosphate ions in water and preparation method thereof |
| CN114725614A (en) * | 2022-04-24 | 2022-07-08 | 扬州大学 | Diaphragm coating material of lithium-sulfur battery and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105618060A (en) * | 2015-12-20 | 2016-06-01 | 青岛科技大学 | Bi-functional oxygen catalyst for graphene/nickel iron type hydrotalcite as well as preparation method and application thereof |
| CN105731606A (en) * | 2016-03-24 | 2016-07-06 | 大连理工大学 | Method for treating organic wastewater through synergistic activation of persulfate using electrochemistry and Ni-Fe-LDH/rGO catalyst |
| CN106513029A (en) * | 2016-12-06 | 2017-03-22 | 武汉工程大学 | Preparation method for metal nanoparticle-loaded nitrogen-doped porous graphene |
| CN106865625A (en) * | 2017-02-14 | 2017-06-20 | 黑龙江大学 | A kind of nanometer sheet being made up of transition metal oxide nano-particles and preparation method thereof |
| CN107376958A (en) * | 2017-06-05 | 2017-11-24 | 国家纳米科学中心 | The difunctional transition metal phosphide catalysts of NiFeP and its preparation and use |
| CN109012675A (en) * | 2018-08-14 | 2018-12-18 | 青岛科技大学 | The method that one-step method prepares the difunctional VPO catalysts of graphene/nickel iron acrylic/hydrotalcite-like nano piece |
-
2019
- 2019-11-26 CN CN201911173612.XA patent/CN111068726A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105618060A (en) * | 2015-12-20 | 2016-06-01 | 青岛科技大学 | Bi-functional oxygen catalyst for graphene/nickel iron type hydrotalcite as well as preparation method and application thereof |
| CN105731606A (en) * | 2016-03-24 | 2016-07-06 | 大连理工大学 | Method for treating organic wastewater through synergistic activation of persulfate using electrochemistry and Ni-Fe-LDH/rGO catalyst |
| CN106513029A (en) * | 2016-12-06 | 2017-03-22 | 武汉工程大学 | Preparation method for metal nanoparticle-loaded nitrogen-doped porous graphene |
| CN106865625A (en) * | 2017-02-14 | 2017-06-20 | 黑龙江大学 | A kind of nanometer sheet being made up of transition metal oxide nano-particles and preparation method thereof |
| CN107376958A (en) * | 2017-06-05 | 2017-11-24 | 国家纳米科学中心 | The difunctional transition metal phosphide catalysts of NiFeP and its preparation and use |
| CN109012675A (en) * | 2018-08-14 | 2018-12-18 | 青岛科技大学 | The method that one-step method prepares the difunctional VPO catalysts of graphene/nickel iron acrylic/hydrotalcite-like nano piece |
Non-Patent Citations (4)
| Title |
|---|
| DAO-CHENG XIA ET AL.: "Graphene/Ni–Fe layered double-hydroxide composite as highly active electrocatalyst for water oxidation", 《MATERIALS RESEARCH BULLETIN》 * |
| NASSER A. M. BARAKAT ET AL.: "Stable N-doped & FeNi-decorated graphene non-precious electrocatalyst for Oxygen Reduction Reaction in Acid Medium", 《SCIENTIFIC REPORTS》 * |
| SUSANGINEE NAYAK ET AL.: "Deciphering Z-scheme Charge transfer Dynamics in Heterostructure NiFe-LDH/N-rGo/g-C3N4 Nanocomposite for photocatalytic pollutant Removal and Water splitting Reactions", 《NATURE》 * |
| 石敏等: "氮掺杂石墨烯的制备及其氧还原电催化性能", 《河南师范大学学报（自然科学版）》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113769759A (en) * | 2021-09-23 | 2021-12-10 | 深圳市康弘环保技术有限公司 | Room-temperature catalytic formaldehyde oxidation composite material, preparation method thereof and air purifier |
| CN114229969A (en) * | 2021-12-30 | 2022-03-25 | 山西诺沃科技有限公司 | Electronic control ionic membrane material for separating phosphate ions in water and preparation method thereof |
| CN114725614A (en) * | 2022-04-24 | 2022-07-08 | 扬州大学 | Diaphragm coating material of lithium-sulfur battery and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sun et al. | Recent progress with electrocatalysts for urea electrolysis in alkaline media for energy-saving hydrogen production | |
| Wang et al. | Recent advances in carbon substrate supported nonprecious nanoarrays for electrocatalytic oxygen evolution | |
| Zhao et al. | Highly efficient metal–organic-framework catalysts for electrochemical synthesis of ammonia from N 2 (air) and water at low temperature and ambient pressure | |
| CN108754531B (en) | Preparation method of Co-and Ru-containing bimetallic carbon nano composite electro-catalytic material | |
| CN111155146B (en) | Preparation method of vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material | |
| CN111068726A (en) | Preparation method of iron-doped nickel phosphide composite nitrogen-doped reduced graphene oxide electrocatalytic material | |
| CN113549935B (en) | Heteroatom-doped transition metal monoatomic catalyst and preparation method and application thereof | |
| CN112108160A (en) | Preparation method of dodecahedron hollow cobalt nickel selenide/iron oxyhydroxide composite catalyst | |
| CN112058287B (en) | In-situ preparation method of two-dimensional metal selenide @ MXene composite electrocatalyst | |
| CN113908870B (en) | Controllable preparation of double-function non-noble metal nitride catalyst and high-current electrolytic urea hydrogen production application | |
| CN111468120B (en) | CoFeNiO X Layered hollow nanocage electrocatalyst and preparation method and application thereof | |
| CN115491712A (en) | Preparation method and application of high-entropy alloy catalyst with porous structure | |
| CN113512738B (en) | Ternary iron-nickel-molybdenum-based composite material water electrolysis catalyst, and preparation method and application thereof | |
| CN117187856A (en) | Preparation method of bifunctional phosphide catalyst and full water decomposition application thereof | |
| CN111672520A (en) | Amorphous cobalt borate-nickel selenide @ foam nickel compound, preparation method and application | |
| CN108963283B (en) | High-dispersion load type core-shell structure Pd @ Ni/WC direct alcohol fuel cell catalyst and preparation method thereof | |
| CN111068695A (en) | Preparation method of multi-metal phosphorus-doped electrocatalyst derived based on ternary LDH | |
| CN114395765B (en) | High-stability alkaline solution hydrogen evolution electrocatalyst and preparation method and application thereof | |
| CN113774425B (en) | Preparation method and application of Ru-modified FeCo @ NF electrocatalyst | |
| CN112779550B (en) | Three-dimensional micron tubular hydrogen evolution reaction electrocatalyst and preparation method thereof | |
| CN115161691A (en) | Oxygen evolution catalyst of FeCoNiMg high-entropy amorphous alloy powder and preparation method thereof | |
| CN115094442B (en) | Preparation method and application of copper-nickel bi-metal nitrogen-carbon material | |
| CN113955728B (en) | Preparation of cobalt phosphide/cobalt manganese phosphide with hollow grade structure and application of electrolytic water | |
| CN114318408B (en) | Self-supporting Cu 3 P-based heterojunction electrocatalyst and preparation method and application thereof | |
| CN114892206B (en) | Multi-metal nitride heterojunction nanorod array composite electrocatalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200428 |
|
| WD01 | Invention patent application deemed withdrawn after publication |