CN117772244A - Core-shell nanowire FeOOH@CoMnP composite material and preparation method and application thereof - Google Patents
Core-shell nanowire FeOOH@CoMnP composite material and preparation method and application thereof Download PDFInfo
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- CN117772244A CN117772244A CN202311740601.1A CN202311740601A CN117772244A CN 117772244 A CN117772244 A CN 117772244A CN 202311740601 A CN202311740601 A CN 202311740601A CN 117772244 A CN117772244 A CN 117772244A
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- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 239000011258 core-shell material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910002588 FeOOH Inorganic materials 0.000 title claims abstract 10
- 239000002070 nanowire Substances 0.000 title description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 106
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 53
- 239000006260 foam Substances 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000004140 cleaning Methods 0.000 claims abstract description 13
- 239000010941 cobalt Substances 0.000 claims abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 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 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 239000011572 manganese Substances 0.000 claims abstract description 8
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 8
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 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
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims 1
- 238000007781 pre-processing Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005868 electrolysis reaction Methods 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000463 material Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000001000 micrograph Methods 0.000 description 6
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002110 nanocone Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The inventionThe invention discloses a core-shell nanowire-shaped FeOOH@CoMnP composite material and a preparation method and application thereof. The preparation method comprises the following steps: sequentially adding a cobalt source, a manganese source, an additive and a reactive auxiliary agent into deionized water, uniformly stirring to form a precursor solution, transferring into a reaction tank, simultaneously adding foam nickel, sealing, placing into a muffle furnace for hydrothermal synthesis reaction, cooling along with the furnace after the reaction is finished, and then cleaning and drying; under the protection of inert atmosphere, respectively placing the obtained nickel foam loaded with cobalt-manganese compound and sodium hypophosphite at a lower tuyere and an upper tuyere of a tube furnace, performing calcination and phosphating reaction, immersing the reaction product into FeCl at normal temperature 3 Adding H dropwise into the solution 2 O 2 And (5) after the solution is fully reacted, cleaning and drying to obtain the catalyst. The composite material prepared by the invention has lower oxygen evolution overpotential and good long-time stability, and can be applied to the fields of hydrogen production and oxygen production by water electrolysis and metal air batteries.
Description
Technical Field
The invention belongs to the technical field of novel functional nano materials, and particularly relates to a core-shell nanowire-shaped FeOOH@CoMnP composite material, and a preparation method and application thereof.
Background
The exhaustion crisis of fossil energy and the aggravation of environmental pollution are promoted, so that scientific researchers are promoted to develop renewable clean energy so as to relieve the crisis of energy and improve the environmental problem. In the emerging renewable clean energy industry, hydrogen production by electrolysis of water is considered a promising technology. However, the efficiency of water electrolysis to produce hydrogen is greatly limited by the rate at which the Oxygen Evolution Reaction (OER) occurs at the anode. Iridium oxide (IrO) has been reported in studies 2 ) And ruthenium oxide (RuO) 2 ) Precious metals are the most efficient catalysts, but the expensive cost and limited reserves make it impractical to scale up. Transition metals are attracted due to unique electronic structuresThe diversity of the attached sites is an ideal alternative catalyst. At present, the catalytic efficiency and long-term stability of most catalysts with single structures cannot meet the requirements of industrial production and application, and research hotspots are mainly focused on the aspects of multi-structure recombination to improve the catalytic efficiency and increase the stability.
Disclosure of Invention
Aiming at the defects of the existing method, the invention provides a core-shell nanowire-shaped FeOOH@CoMnP composite material, and a preparation method and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a core-shell nanowire-shaped FeOOH@CoMnP composite material comprises the following steps:
step 1: sequentially adding a cobalt source, a manganese source, an additive and a coagent into deionized water, and uniformly stirring to form a precursor solution;
step 2: transferring the precursor solution obtained in the step 1 into a reaction tank, adding foam nickel at the same time, sealing, then placing in a muffle furnace for hydrothermal synthesis reaction, cooling along with the furnace after the reaction is finished, and then cleaning and drying the foam nickel after the reaction;
step 3: under the protection of inert atmosphere, respectively placing the foamed nickel loaded with the cobalt-manganese compound and sodium hypophosphite obtained in the step 2 into a lower tuyere and an upper tuyere of a tube furnace for calcination and phosphating reaction;
step 4: immersing the product obtained in the step 3 into FeCl at normal temperature by adopting a chemical bath method 3 Adding H dropwise into the solution 2 O 2 And (3) after the solution is fully reacted, cleaning and drying to obtain a target product.
Preferably, in the step 1, the cobalt source is one or more of cobalt oxalate, cobalt chloride, cobalt nitrate and cobalt sulfate, and the molar concentration of the cobalt source in the precursor solution is 0.01-0.1 mol/L.
Preferably, the manganese source in the step 1 is one or more of manganese oxalate, manganese chloride, manganese nitrate and manganese sulfate, and the molar concentration of the manganese source in the precursor solution is 0.001-0.05 mol/L.
Preferably, the additive in the step 1 is ammonium fluoride, and the concentration of ammonium chloride in the precursor solution is 0.01-0.5 mol/L; the active auxiliary agent is urea, and the concentration of the urea in the precursor solution is 0.05-0.5 mol/L.
Preferably, the nickel foam in step 2 is subjected to pretreatment before being added, wherein the pretreatment is ultrasonic cleaning by sequentially using hydrochloric acid, absolute ethyl alcohol and deionized water, and then drying treatment.
Preferably, the hydrothermal synthesis reaction in the step 2 is performed by heating to 100-160 ℃ at a heating rate of 5-15 ℃/min, and preserving heat for 1-12 h.
Preferably, the mass ratio of the sodium hypophosphite in the step 3 to the foam nickel in the step 2 is 2-5: and 1, heating to 300-400 ℃ at the temperature rising rate of 1-5 ℃/min, and calcining for 1-3 h.
Preferably, the FeCl in step 4 3 The concentration of the solution is 0.05 to 0.1mol/L, and the FeCl 3 The dosage ratio of the solution to the foam nickel in the step 2 is 20-30 mL:0.1g of said H 2 O 2 The dosage ratio of the solution to the foam nickel in the step 2 is 5-10 mL:0.1g, and the reaction time is 0.5-5 min.
The core-shell nanowire-shaped FeOOH@CoMnP composite material prepared by the preparation method.
The core-shell nanowire-shaped FeOOH@CoMnP composite material prepared by the preparation method is applied to an electrolytic water oxygen evolution reaction catalyst.
The invention has the positive beneficial effects that:
1. the invention adopts the foam nickel as the matrix, the foam nickel has large specific surface area of three-dimensional network structure, and the surface of the crystal grain is smooth and flat, which is beneficial to the uniform nucleation and growth of cobalt and manganese ions on the surface of the crystal grain. The invention prepares the catalytic material directly on the foam nickel substrate, avoids the use of binder and conductive agent, and has simple and convenient process and low cost.
2. In the invention, ammonium fluoride and urea are added in the hydrothermal synthesis reaction process to promote the reaction and nano-size control, promote the nucleation of cobalt-manganese layered double hydroxide, and the ammonium fluoride reacts with water to gradually generate OH - Controlling cobalt and manganese ionsThe method can stabilize and nucleate uniformly on the surface of the foam nickel, and compared with the traditional method of directly adding precipitants such as NaOH, KOH and the like, cobalt and manganese ions quickly nucleate and grow in a short time, so that the technical problem that the cobalt and manganese ions are difficult to control and nucleate stably on the surface of the foam nickel, and the morphology structure is uncontrollable is solved, and the prepared cobalt and manganese compound has uniform particle size and consistent morphology structure.
3. According to the invention, the cobalt manganese phosphide CoMnP composite material is obtained through calcination and phosphating reaction, then a chemical bath method is adopted, hydrogen peroxide has a strong oxidation effect, feOOH is quickly deposited on the surface of cobalt manganese phosphide CoMnP in extremely short reaction time, the FeOOH has excellent catalytic performance on oxygen evolution reaction, is embedded on CoMnP nanowires, forms a hierarchical nano array structure which directly grows on a foam nickel conductive substrate, can increase the specific surface area of the catalyst, alleviate the volume change capability, and is doped with hetero atoms to provide more electroactive sites and regulate and control electronic structures; the FeOOH thin layer has the thickness of 0.5-5 nm, has more abundant and sufficient active sites due to the excellent conductivity of the CoMnP carrier and the small-size effect of the FeOOH thin layer, is favorable for electron transport, and Fe 3+ Ion and Co 2+ Ion, mn 2+ Ion formation synergistic catalysis enhancement effect, and the overpotential of oxygen evolution reaction is obviously reduced by using the obtained electrocatalyst FeOOH@CoMnP in a test environment of 1mol/L KOH solution, and the overpotential of oxygen evolution reaction is 10mA cm -2 The overpotential at the current density of (2) is only 220mV, and the Tafil slope is 65.21 mV.dec -1 Has excellent electrochemical performance. Meanwhile, feOOH ultrafine nano particles are fixed on the CoMnP nanowire carrier to prevent agglomeration and decay of the FeOOH@CoMnP, so that the FeOOH@CoMnP has long-term stability exceeding 40 hours, can be used as a catalyst material for hydrogen production, oxygen production and metal-air batteries by water electrolysis, and has wide application prospects in the fields of energy conversion, storage and the like.
Drawings
FIG. 1 is a graphical representation of FeOOH@CoMnP composite material and nickel foam prepared in example 1; wherein: a is foam nickel pretreated in the step 2 of the example 1, and b is FeOOH@CoMnP composite material prepared in the example 1;
FIG. 2 is a scanning electron microscope image of the CoMnP material prepared in comparative example 1;
FIG. 3 is a scanning electron microscope image of the FeOOH material prepared in comparative example 2;
FIG. 4 is a scanning electron microscope image of the FeOOH@CoMnP composite material prepared in example 1;
FIG. 5 is a transmission electron microscope image of the FeOOH@CoMnP composite material prepared in example 1;
FIG. 6 is an X-ray diffraction pattern of the FeOOH@CoMnP composite material prepared in example 1;
FIG. 7 is a LSV graph of oxygen evolution reaction of FeOOH@CoMnP composite material prepared in example 1 and CoMnP of comparative example 1, feOOH material of comparative example 2 in alkaline environment;
FIG. 8 is a Tafel slope plot of oxygen evolution reaction of FeOOH@CoMnP composite material prepared in example 1 and CoMnP of comparative example 1, feOOH material of comparative example 2 in alkaline environment;
FIG. 9 is a graph showing that the FeOOH@CoMnP composite material prepared in example 1 was prepared in an alkaline environment of 10mA.cm- 2 An i-t stability test plot in oxygen evolution reactions at current density;
FIG. 10 shows the FeOOH@CoMnP composite material prepared in example 1 in an alkaline environment of 10-100 mA cm- 2 A step i-t stability test plot in an oxygen evolution reaction at current density;
FIG. 11 shows the oxygen evolution reaction double layer capacitance C of FeOOH@CoMnP composite material prepared in example 1, coMnP of comparative example 1, feOOH material of comparative example 2 in alkaline environment dl A graph;
FIG. 12 is an EIS curve of FeOOH@CoMnP composite material prepared in example 1, coMnP of comparative example 1, feOOH material of comparative example 2 under alkaline environment;
FIG. 13 is an enlarged scale of 1X 10 of the FeOOH@CoMnP composite material prepared in example 2 4 A scanning electron microscope image of the multiple;
FIG. 14 is an enlarged scale of 1X 10 of the FeOOH@CoMnP composite material prepared in example 2 5 Multiple scanning electron microscope images.
Detailed Description
For a better understanding of the present invention, the following description is made in detail with reference to examples and accompanying drawings, but the embodiments and the scope of the present invention are not limited thereto.
Example 1
A preparation method of a core-shell nanowire-shaped FeOOH@CoMnP composite material comprises the following steps:
(1) 0.3850g of cobalt nitrate hexahydrate, 0.0212g of manganese sulfate monohydrate, 0.8882g of ammonium fluoride and 0.22g of urea are dissolved in 50mL of deionized water, the molar concentrations are respectively 0.026mol/L, 0.0025mol/L, 0.48mol/L and 0.073mol/L, and the solution is stirred by magnetic force for 20min at the stirring speed of 200r/min, and then precursor solution is obtained after uniform stirring;
(2) Taking foam nickel with the size of 1cm multiplied by 4cm multiplied by 0.16cm and the density of 0.42 g.cm -3 Respectively ultrasonically cleaning with 1mol/L hydrochloric acid solution, absolute ethyl alcohol and deionized water for 5min, drying at normal temperature for 12h to remove greasy dirt and oxide on the surface of foam nickel, obtaining pretreated foam nickel, placing the pretreated foam nickel into the precursor solution in the step (1) with the weight of 0.1g, transferring the treated foam nickel into a polytetrafluoroethylene tank with the weight of 100mL, preparing a PVA outer tank, sealing and fastening, heating to 120 ℃ in a muffle furnace at a heating rate of 10 ℃/min, preserving heat for 6h, cooling along with the furnace after the reaction is finished, cleaning the reacted foam nickel with deionized water for 3 times, and drying at normal temperature for 12h;
(3) Under inert atmosphere, respectively placing the nickel foam loaded with the cobalt-manganese compound and the sodium hypophosphite, which are obtained in the step (2), in a lower tuyere and an upper tuyere of a tube furnace, heating to 350 ℃ at a heating rate of 5 ℃/min, and calcining for 3 hours;
(4) Immersing the product obtained in the step (3) into FeCl with the concentration of 0.1mol/L and the volume of 20mL by adopting a chemical bath method 3 To the solution, 5mL of H was added dropwise 2 O 2 And (3) after reacting for 0.5min, washing the solution with deionized water for 3 times, and drying the solution at normal temperature for 12h to obtain a target product.
Comparative example 1
A method for preparing a CoMnP composite material, comprising the steps of:
(1) 0.3850g of cobalt nitrate hexahydrate, 0.0212g of manganese sulfate monohydrate, 0.8882g of ammonium fluoride and 0.22g of urea are dissolved in 50mL of deionized water, the molar concentrations are respectively 0.026mol/L, 0.0025mol/L, 0.48mol/L and 0.073mol/L, and the solution is stirred by magnetic force for 20min at the stirring speed of 200r/min, and then precursor solution is obtained after uniform stirring;
(2) Taking foam nickel with the size of 1cm multiplied by 4cm multiplied by 0.16cm and the density of 0.42 g.cm -3 Respectively ultrasonically cleaning with 1mol/L hydrochloric acid solution, absolute ethyl alcohol and deionized water for 5min, drying at normal temperature for 12h to remove greasy dirt and oxide on the surface of foam nickel, obtaining pretreated foam nickel, placing the pretreated foam nickel into the precursor solution in the step (1) with the weight of 0.1g, transferring the treated foam nickel into a polytetrafluoroethylene tank with the weight of 100mL, preparing a PVA outer tank, sealing and fastening, heating to 120 ℃ in a muffle furnace at a heating rate of 10 ℃/min, preserving heat for 6h, cooling along with the furnace after the reaction is finished, cleaning the reacted foam nickel with deionized water for 3 times, and drying at normal temperature for 12h;
(3) And (3) respectively placing the foam nickel loaded with the nano material and 0.5g of sodium hypophosphite obtained in the step (2) in a lower tuyere and an upper tuyere of a tube furnace under the condition of a heating rate of 5 ℃/min, heating to 350 ℃, and calcining for 3 hours to obtain the CoMnP target product.
Comparative example 2
A method for preparing an iron oxyhydroxide (FeOOH) material, comprising the steps of:
(1) Taking foam nickel with the size of 1cm multiplied by 4cm multiplied by 0.16cm and the density of 0.42 g.cm -3 Respectively ultrasonically cleaning with 1mol/L hydrochloric acid solution, absolute ethyl alcohol and deionized water for 5min, and drying at normal temperature for 12h to remove greasy dirt and oxide on the surface of the foam nickel to obtain pretreated foam nickel, wherein the weight of the pretreated foam nickel is 0.1g;
(2) Immersing the pretreated foam nickel into FeCl with the concentration of 0.1mol/L and the volume of 20mL 3 To the solution, 5mL of H was added dropwise 2 O 2 And (3) after the solution fully reacts for 0.5min, washing the solution with deionized water for 3 times, and drying the solution at normal temperature for 12h to obtain a ferric hydroxide (FeOOH) product.
FIG. 1 is a graphical representation of the pretreated nickel foam and FeOOH@CoMnP material of example 1, and it can be seen from FIG. 1 that the pretreated nickel foam in graph a is in a medium gray color, the foam pores are obvious, and the reacted nickel foam in graph b has deposited reaction products on the surface, the color of which has been changed to black-brown color, and no other changes.
As can be seen from FIG. 2, the CoMnP obtained in comparative example 1 has a uniform particle size, a nanowire shape, a smooth surface and a uniform structure.
As is clear from FIG. 3, feOOH obtained in comparative example 2 was in an amorphous state and was connected in one piece.
As can be seen from fig. 4, the feooh@comnp composite material obtained in example 1 is a coated nanowire, and the nanowire surface is rough.
From the transmission electron microscope picture of the FeOOH@CoMnP composite material obtained in example 1 of FIG. 5, it can be seen that the sample is in a nanowire shape, the particle size of the inner core nanowire is about 50nm, a coating is externally attached, and the thickness of the coating is about 15-20 nm.
FIG. 6 is an XRD pattern of the FeOOH@CoMnP composite material prepared in example 1, wherein the FeOOH@CoMnP composite material has obvious main diffraction peaks corresponding to CoP and MnP, but the 2 theta angles corresponding to different crystal planes of FeOOH are not obviously detected, and the composite material is amorphous.
As is clear from FIG. 7, in 1mol/L KOH solution, without IR compensation, it is evident that the oxygen evolution overpotential of FeOOH@CoMnP is significantly lower than that of the comparative examples FeOOH and CoMnP, at a transmission of 10 mA.cm -2 The oxygen evolution overpotential required is only 220mV, which is significantly lower than that of the CoMnP and FeOOH of the comparative example, indicating that the FeOOH@CoMnP composite material has good oxygen evolution reaction catalytic capability.
As is clear from FIG. 8, the FeOOH@CoMnP prepared in example 1 has a Tafil slope of 65.21 mV.dec -1 86.03 mV.dec significantly less than FeOOH -1 And 126.59 mV.dec of CoMnP -1 The FeOOH@CoMnP composite material disclosed by the invention has the advantages of higher electron migration rate and good oxygen evolution reaction catalytic capability.
As is clear from FIG. 9, the FeOOH@CoMnP composite material obtained in example 1 has a long-term stability and a current of 10 mA.cm -2 And the oxygen evolution reaction potential is stabilized at 1.45V for more than 40h.
As can be seen from FIG. 10, the FeOOH@CoMnP complex obtained in example 1The step time stability of the composite material is between 10 and 100mA cm when the current is transmitted -2 When the oxygen evolution overpotential of the sample is carried out, the sample can be kept stable in each stage, and no performance reduction occurs, so that the FeOOH@CoMnP composite material has excellent electrical stability.
As can be seen from FIG. 11, example 1 produced C dl Layered double capacitance of FeOOH@CoMnP is 18.57 mF.cm -2 9.07 mF.cm significantly higher than that of the comparative example FeOOH -2 And 6.51 mF.cm of CoMnP -2 The FeOOH@CoMnP composite material is demonstrated to have a larger electrochemical active area.
From the EIS curve of fig. 12, the charge transfer resistance of feooh@comnp is significantly reduced, indicating that the feooh@comnp composite material has a faster electron conducting capability.
Example 2
A preparation method of a core-shell nanowire-shaped FeOOH@CoMnP composite material comprises the following steps:
(1) 0.4657g of cobalt nitrate hexahydrate, 0.0676g of manganese sulfate monohydrate, 0.0703g of ammonium fluoride and 0.6006g of urea are dissolved in 50mL of deionized water, the molar concentration is 0.032mol/L, 0.0080mol/L, 0.038mol/L and 0.2mol/L respectively, and the solution is stirred by magnetic force for 20min at the stirring speed of 200r/min, and then precursor solution is obtained after uniform stirring;
(2) Taking foam nickel with the size of 1cm multiplied by 4cm multiplied by 0.16cm and the density of 0.42 g.cm -3 Respectively ultrasonically cleaning with 1mol/L hydrochloric acid solution, absolute ethyl alcohol and deionized water for 5min, drying at normal temperature for 12h to remove greasy dirt and oxide on the surface of foam nickel, obtaining pretreated foam nickel, placing 0.12g of pretreated foam nickel into the precursor solution in the step (1), transferring the pretreated foam nickel into a polytetrafluoroethylene tank with 100mL, configuring a PVA outer tank, sealing and fastening, heating to 120 ℃ in a muffle furnace at a heating rate of 10 ℃/min, preserving heat for 3h, cooling along with the furnace after the reaction is finished, cleaning the reacted foam nickel with deionized water for 3 times, and drying at normal temperature for 12h;
(3) In inert N 2 Under the atmosphere, the foam nickel loaded with the nano material and obtained in the step (2) and 0.3g of sodium hypophosphite are respectively placed at the lower tuyere and the lower tuyere of a tube furnaceAnd heating to 400 ℃ at a heating rate of 5 ℃/min at an upper tuyere, and calcining for 3 hours.
(4) Immersing the product obtained in the step (3) into FeCl with the concentration of 0.1mol/L and the volume of 30mL by adopting a chemical bath method 3 To the solution, 10mL of H was added dropwise 2 O 2 And (3) after the solution fully reacts for 2min, washing the solution with deionized water for 3 times, and drying the solution at normal temperature for 12h to obtain a target product.
Fig. 13 and 14 are SEM images of feooh@comnp prepared in example 2, from which it is known that the obtained feooh@comnp composite material is a nanowire morphology structure and forms multiple bundles of cross-linked, nano-cone morphology, which is rough in surface, has a scale-like coating, contains more catalytic active sites, and is beneficial to improving the electrocatalytic efficiency of the sample.
Example 3
The core-shell nanowire-shaped FeOOH@CoMnP composite material prepared by the preparation method of the embodiment 1 or 2.
The application of the core-shell nanowire-shaped FeOOH@CoMnP composite material prepared by the preparation method of the embodiment 1 or 2 as an electrolytic water oxygen evolution reaction catalyst.
Finally, it is noted that the above-mentioned embodiments are merely for illustrating the technical solution of the present invention, and that other modifications and equivalents thereof by those skilled in the art should be included in the scope of the claims of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the core-shell nanowire-shaped FeOOH@CoMnP composite material is characterized by comprising the following steps of:
step 1: sequentially adding a cobalt source, a manganese source, an additive and a coagent into deionized water, and uniformly stirring to form a precursor solution;
step 2: transferring the precursor solution obtained in the step 1 into a reaction tank, adding foam nickel at the same time, sealing, then placing in a muffle furnace for hydrothermal synthesis reaction, cooling along with the furnace after the reaction is finished, and then cleaning and drying the foam nickel after the reaction;
step 3: under the protection of inert atmosphere, the foamed nickel loaded with the cobalt-manganese compound and sodium hypophosphite obtained in the step 2 are respectively placed in a lower tuyere and an upper tuyere of a tube furnace for calcination and phosphating reaction;
step 4: immersing the product obtained in the step 3 into FeCl at normal temperature by adopting a chemical bath method 3 Adding H dropwise into the solution 2 O 2 And (3) after the solution is fully reacted, cleaning and drying to obtain a target product.
2. The method for preparing the core-shell nanowire-shaped FeOOH@CoMnP composite material, which is characterized by comprising the following steps of: the cobalt source in the step 1 is one or more of cobalt oxalate, cobalt chloride, cobalt nitrate and cobalt sulfate, and the molar concentration of the cobalt source in the precursor solution is 0.01-0.1 mol/L.
3. The method for preparing the core-shell nanowire-shaped FeOOH@CoMnP composite material, which is characterized by comprising the following steps of: the manganese source in the step 1 is one or more of manganese oxalate, manganese chloride, manganese nitrate and manganese sulfate, and the molar concentration of the manganese source in the precursor solution is 0.001-0.05 mol/L.
4. The method for preparing the core-shell nanowire-shaped FeOOH@CoMnP composite material, which is characterized by comprising the following steps of: the additive in the step 1 is ammonium fluoride, and the concentration of the ammonium fluoride in the precursor solution is 0.01-0.5 mol/L; the active auxiliary agent is urea, and the concentration of the urea in the precursor solution is 0.05-0.5 mol/L.
5. The method for preparing the core-shell nanowire-shaped FeOOH@CoMnP composite material, which is characterized by comprising the following steps of: and 2, preprocessing the foam nickel before adding, namely sequentially using hydrochloric acid, absolute ethyl alcohol and deionized water for ultrasonic cleaning, and then drying.
6. The method for preparing the core-shell nanowire-shaped FeOOH@CoMnP composite material, which is characterized by comprising the following steps of: the hydrothermal synthesis reaction in the step 2 is to heat to 100-160 ℃ under the condition of the heating rate of 5-15 ℃/min, and the reaction is kept for 1-12 h.
7. The method for preparing the core-shell nanowire-shaped FeOOH@CoMnP composite material, which is characterized by comprising the following steps of: the mass ratio of the sodium hypophosphite in the step 3 to the foam nickel in the step 2 is 2-5: and 1, heating to 300-400 ℃ at the temperature rising rate of 1-5 ℃/min, and calcining for 1-3 h.
8. The method for preparing the core-shell nanowire-shaped FeOOH@CoMnP composite material, which is characterized by comprising the following steps of: feCl described in step 4 3 The concentration of the solution is 0.05 to 0.1mol/L, and the FeCl 3 The dosage ratio of the solution to the foam nickel in the step 2 is 20-30 mL:0.1g of said H 2 O 2 The dosage ratio of the solution to the foam nickel in the step 2 is 5-10 mL:0.1g, and the reaction time is 0.5-5 min.
9. A core-shell nanowire-shaped feooh@comnp composite material prepared by the preparation method of any one of claims 1 to 8.
10. Use of a core-shell nanowire-shaped feooh@comnp composite material prepared by the preparation method according to any one of claims 1 to 8 as an electrolytic water oxygen evolution reaction catalyst.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350312A (en) * | 2011-07-19 | 2012-02-15 | 山西大学 | Beta-cyclodextrin functionalized Fe3O4 magnetic nanometer adsorbent and use thereof |
| CN108511202A (en) * | 2018-02-06 | 2018-09-07 | 四川大学 | A kind of preparation method of Mn doping CoP nano wires modification nano-chip arrays hierarchical structure electrode material for super capacitor |
| CN111701607A (en) * | 2020-06-15 | 2020-09-25 | 西北大学 | MnCo2O4@Ni2P/NF difunctional full-hydrolysis catalyst and preparation method and application thereof |
| CN113955728A (en) * | 2021-09-15 | 2022-01-21 | 浙江大学 | Preparation of hollow-grade-structure cobalt phosphide/cobalt manganese phosphide and application of hollow-grade-structure cobalt phosphide/cobalt manganese phosphide in electrolytic water |
| CN116555806A (en) * | 2023-03-16 | 2023-08-08 | 明阳智慧能源集团股份公司 | Preparation method and application of foam nickel-loaded sea urchin-shaped phosphorus-doped catalyst |
| US20230332307A1 (en) * | 2022-04-13 | 2023-10-19 | Iowa State University Research Foundation, Inc. | System and methods for low-voltage bipolar hydrogen production from aldehydes and water |
| CN117107289A (en) * | 2023-08-28 | 2023-11-24 | 安阳师范学院 | Kennel-shaped nickel cobaltate@iron oxyhydroxide hierarchical nano-array catalyst material |
-
2023
- 2023-12-18 CN CN202311740601.1A patent/CN117772244A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102350312A (en) * | 2011-07-19 | 2012-02-15 | 山西大学 | Beta-cyclodextrin functionalized Fe3O4 magnetic nanometer adsorbent and use thereof |
| CN108511202A (en) * | 2018-02-06 | 2018-09-07 | 四川大学 | A kind of preparation method of Mn doping CoP nano wires modification nano-chip arrays hierarchical structure electrode material for super capacitor |
| CN111701607A (en) * | 2020-06-15 | 2020-09-25 | 西北大学 | MnCo2O4@Ni2P/NF difunctional full-hydrolysis catalyst and preparation method and application thereof |
| CN113955728A (en) * | 2021-09-15 | 2022-01-21 | 浙江大学 | Preparation of hollow-grade-structure cobalt phosphide/cobalt manganese phosphide and application of hollow-grade-structure cobalt phosphide/cobalt manganese phosphide in electrolytic water |
| US20230332307A1 (en) * | 2022-04-13 | 2023-10-19 | Iowa State University Research Foundation, Inc. | System and methods for low-voltage bipolar hydrogen production from aldehydes and water |
| CN116555806A (en) * | 2023-03-16 | 2023-08-08 | 明阳智慧能源集团股份公司 | Preparation method and application of foam nickel-loaded sea urchin-shaped phosphorus-doped catalyst |
| CN117107289A (en) * | 2023-08-28 | 2023-11-24 | 安阳师范学院 | Kennel-shaped nickel cobaltate@iron oxyhydroxide hierarchical nano-array catalyst material |
Non-Patent Citations (3)
| Title |
|---|
| JIANLIN CHENG等: "FeOOH decorated CoP porous nanofiber for enhanced oxygen evolution activity", 《CHEMICAL ENGINEERING JOURNAL》, vol. 428, 31 January 2022 (2022-01-31), pages 131130 * |
| 程建林: "钴基过渡金属磷化物纳米材料的制备及其电催化性能的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, 15 December 2021 (2021-12-15), pages 35 - 36 * |
| 陈聪地;侯天武;黄琼;李秉轲;王洁雪;杨敏;: "Co_3O_4@MnCo_2O_4纳米材料的合成及其性能研究", 广州化工, no. 08, 23 April 2018 (2018-04-23), pages 52 - 55 * |
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