CN110479328B - Fe-doped cobalt hydroxyphosphite nanosheet array structure material and preparation method and application thereof - Google Patents
Fe-doped cobalt hydroxyphosphite nanosheet array structure material and preparation method and application thereof Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 84
- 239000000463 material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- -1 cobalt hydroxyphosphite Chemical compound 0.000 title description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 72
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 31
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 12
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 150000002505 iron Chemical class 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000012046 mixed solvent Substances 0.000 claims abstract description 4
- 238000004729 solvothermal method Methods 0.000 claims abstract description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 9
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 1
- 239000006260 foam Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 9
- 239000000758 substrate Substances 0.000 abstract description 4
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- 230000010287 polarization Effects 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 11
- 238000004502 linear sweep voltammetry Methods 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000002064 nanoplatelet Substances 0.000 description 7
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000370 acceptor Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 2
- 230000003872 anastomosis Effects 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002060 nanoflake Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical class OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
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Images
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- 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
-
- B01J35/23—
-
- B01J35/33—
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
-
- 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
Dissolving iron salt, cobalt salt and sodium hypophosphite into a mixed solvent of water and isopropanol, transferring the solution into a reaction kettle, obliquely placing foamed nickel into the solution, carrying out solvothermal reaction, cooling to room temperature after the reaction is finished, washing and drying a product to obtain the Fe-doped Co nanosheet array structure material, and a preparation method and application thereof11(HPO3)8(OH)6The invention relates to a nano-sheet array structure material, which designs and synthesizes Fe-doped Co on a nickel foam substrate11(HPO3)8(OH)6The nano-sheet array structure can effectively adjust Co by using Fe doping11(HPO3)8(OH)6The electronic structure reduces the resistance, increases the active sites, improves the hydrophilicity and accelerates the electron transfer rate, and the Fe is doped with Co11(HPO3)8(OH)6The nanosheet array structure material is used as an electrocatalyst for oxygen evolution reaction, hydrogen evolution reaction and full-water decomposition reaction, has the advantages of high activity, good durability, simple preparation process and low cost, and has a great value in researching the practical application of water decomposition electrocatalyst materials.
Description
Technical Field
The invention belongs to the field of a preparation method of a nano material and electrocatalysis application, and particularly relates to a Fe-doped cobalt hydroxyphosphite nanosheet array structure material as well as a preparation method and application thereof.
Background
The electrolysis of water to produce hydrogen and oxygen provides a promising approach for renewable energy storage. The key of the technology is to develop an electrocatalyst with high activity, durability and economic characteristics to realize the high-efficiency performance of two half reactions of Oxygen Evolution (OER) and Hydrogen Evolution (HER). As is well known, IrO2And RuO2Are considered advanced OER catalysts, while Pt-based materials are advanced HER catalysts. However, the high cost and poor durability of these noble metal catalysts have severely hampered their large-scale use. Therefore, it is necessary to find an electrocatalyst having a low overpotential and high durability from materials rich in global resources.
In recent years, 3d transition metal (e.g., Ni, Co, Fe and Mn) phosphates have become a class of electrocatalysts for bifunctional, especially OER reactions, effective in neutral and alkaline media. The different coordination configurations and structure types of the transition metal phosphate can stabilize the intermediate state of the metal center, and more importantly, the phosphate can be used as a proton carrier to accelerate protons (H)+) And the stable local pH environment is maintained, so that the OER catalytic activity is greatly improved. The rich oxygen element in the phosphate radical provides more active sites for water adsorption and is beneficial to oxygen precipitation. In addition, the transition metal metaphosphates and hydrogenphosphates carry PO separately3 −Or HPO4 2−Proton acceptors can also be used for OER electrocatalysis, while hydroxyl is another type of proton acceptor and hydroxyl phosphates have different proton acceptors with the hope of improving the catalytic activity of water decomposition.
Transition metal cobalt hydroxyphosphite Co11(HPO3)8(OH)6By MO6The octahedron shared edges and corners have a three-dimensional octahedron array structure, and triangular and hexagonal channels are arranged along the C-axis direction. The unique micropore channel can effectively expose active sites to electrolyte, realizes rapid interface charge transfer, and becomes a multipurpose energy storage electrode material.
Although cobalt hydroxyphosphite Co11(HPO3)8(OH)6Has good application prospect, however, the cobalt hydroxyphosphite Co in the prior art11(HPO3)8(OH)6The preparation method is complex and has low catalytic activity.
Disclosure of Invention
In order to solve the technical problems, the invention provides a Fe-doped cobalt hydroxyphosphite nanosheet array structure material and a preparation method thereofA preparation method and application thereof. Fe-doped Co supported on a foamed nickel substrate is prepared through one-step liquid phase solvothermal reaction11(HPO3)8(OH)6Nanoplate array structured materials that are applicable to OER, HER and total moisture applications. In Co11(HPO3)8(OH)6In the nano-sheet, two proton acceptors of hydroxyl and phosphite can accelerate the proton transfer and electron movement, and the introduced foreign metal cation Fe3+Can effectively regulate Co11(HPO3)8(OH)6The electronic structure improves hydrophilicity, accelerates electron transfer rate, enhances conductivity, increases active sites, and realizes outstanding electrocatalytic water decomposition activity and stability.
The invention provides Fe doped Co11(HPO3)8(OH)6The preparation method of the nano-sheet array structure material comprises the following steps:
dissolving iron salt, cobalt salt and hypophosphite in a mixed solvent of water and isopropanol, transferring the solution to a reaction kettle, obliquely placing foamed nickel in the solution, carrying out solvothermal reaction, cooling to room temperature after the reaction is finished, washing and drying a product to obtain the Fe-doped Co11(HPO3)8(OH)6A nanosheet array structure material.
Further, the iron salt is ferric nitrate nonahydrate; the cobalt salt is cobalt nitrate hexahydrate; the hypophosphite is sodium hypophosphite.
The ratio of the amount of the iron salt, the cobalt salt and the hypophosphite is 0.2-0.8: 1-2: 1, and preferably 0.6:1: 1.
The concentration of the hypophosphite in water and isopropanol was 0.025M.
The volume ratio of the solvent water to the isopropanol is 1-2: 3-2, and preferably 1: 3.
The solvent thermal reaction condition is that the reaction is carried out for 4 to 8 hours at 160 ℃, and the reaction is preferably carried out for 6 hours at 160 ℃.
The foam Nickel (NF) needs to be cleaned before use, and the specific cleaning steps are as follows: soaking in 6M hydrochloric acid for 15 min to remove outer oxide film, and cleaning with deionized water and anhydrous ethanol for 3-5 times; when in use, the foam nickel is cut into the size of 2 multiplied by 3 cm.
The washing is 3-5 times by using deionized water and absolute ethyl alcohol respectively.
And the drying is natural airing in an air atmosphere.
The invention also provides Fe-doped Co prepared by the preparation method11(HPO3)8(OH)6A nanosheet array structure material, the Fe being doped with Co11(HPO3)8(OH)6The morphology of the nano-sheet array structure material is composed of nano-sheets with the average size of 300-500 nm, and Fe3+In Co11(HPO3)8(OH)6The nano sheets are uniformly distributed.
The invention also provides the Fe doped Co11(HPO3)8(OH)6The nanosheet array structure material is applied as an electrocatalyst for an oxygen evolution reaction, a hydrogen evolution reaction or a full-water decomposition reaction.
The Fe is doped with Co11(HPO3)8(OH)6When the nano-sheet array structure material is applied as an Oxygen Evolution Reaction (OER) electrocatalyst, the specific method comprises the following steps: doping Fe prepared on foam nickel with Co11(HPO3)8(OH)6The nanosheet array structure material is cut into a size of 0.5 multiplied by 0.5cm to be used as a working electrode, 1M KOH solution is used as electrolyte, and a CHI760E electrochemical workstation is used for testing. Platinum wires and Ag/AgCl electrodes were used as counter and reference electrodes, respectively. Linear Sweep Voltammetry (LSV) at 2.0 mV · s−1The polarization curve is obtained at a scanning rate of 90% with ohmic compensation; stability was obtained by measuring the current density time curve at constant voltage. Electrochemically active area (ECSA) was determined by scanning at different rates (10, 12, 14, 16, 18, 20 and 22 mV · s) without significant faraday regions−1) Measuring the electric double layer capacitance (C) of a capacitordl) Carrying out evaluation; electrochemical Impedance (EIS) open circuit voltage was tested in the frequency range of 100 kHz to 0.1 Hz. And respectively as commercial RuO2And Co11(HPO3)8(OH)6The nanosheets were supported on foamed nickel as working electrodes, and their OER properties were measured separately for comparison.
The Fe is doped with Co11(HPO3)8(OH)6When the nanosheet array structure material is applied as a Hydrogen Evolution Reaction (HER) electrocatalyst, the specific method comprises the following steps: doping Fe prepared on foam nickel with Co11(HPO3)8(OH)6The nanosheet array structure material is cut into 0.5 multiplied by 0.5cm to be used as a working electrode, 1M KOH solution is used as electrolyte, and a CHI760E electrochemical workstation is used for testing. Carbon rods and Ag/AgCl electrodes were used as counter and reference electrodes, respectively. Linear Sweep Voltammetry (LSV) at 2.0 mV · s−1The polarization curve is obtained at a scanning rate of 90% ohm compensation; stability was obtained by measuring the current density time curve at constant voltage. Electrochemically active area (ECSA) was determined by scanning at different rates (10, 12, 14, 16, 18, 20 and 22 mV · s) without significant faraday regions−1) Measuring the electric double layer capacitance (C) of a capacitordl) Carrying out evaluation; electrochemical Impedance (EIS) open circuit voltage was tested in the frequency range of 100 kHz to 0.1 Hz. And as commercial Pt/C and Co, respectively11(HPO3)8(OH)6The nanosheets are loaded on foamed nickel to serve as working electrodes, and the performance of HER is measured respectively for comparison.
The Fe is doped with Co11(HPO3)8(OH)6When the nano-sheet array structure material is used as an electrocatalyst of a full-water decomposition reaction, the specific method comprises the following steps: mixing Fe prepared on foam nickel with Co11(HPO3)8(OH)6The nano-sheet array structure material is cut into 2 pieces with the size of 0.5 multiplied by 0.5cm and respectively used as a cathode and an anode to be assembled in a double-electrode electrolytic cell, and the total hydrolysis performance is tested through an LSV polarization curve compensated by 90% iR and a current density time curve under constant voltage. As a comparison, the noble metal RuO supported on nickel foam in a two-electrode electrolyzer was investigated2LSV polarization curves as anode and Pt/C as cathode.
In the invention, Fe doping regulates the electronic structure of the catalyst and reducesThe resistance is increased, and the electrochemical active area is increased. Fe doped Co11(HPO3)8(OH)6The presence of the defect structure effectively exposes the active sites in the electrolyte solution. The hydroxyl and phosphite proton acceptors can form hydrogen bonds with water molecules, so that the surface has high wettability, and proton and electron can be rapidly transferred. Fe doping causes local Co environment distortion to promote water to be adsorbed to active sites, and the compatibility and affinity of water on the surface of the catalyst are increased. The high hydrophilicity enhances the electrolyte penetration, further enhances the charge transfer rate between the electrolyte and the catalyst, and improves the catalytic activity. Fe doped Co11(HPO3)8(OH)6Defects and distortions existing on the nano-chip bring more open coordination sites for adsorbing reaction intermediates, and the interface charge transfer rate is accelerated. Therefore, the material shows outstanding activity and excellent durability in alkaline electrolyte for oxygen evolution reaction, hydrogen evolution reaction and all-water decomposition reaction, and has great value for researching the practical application of water decomposition electro-catalysis electrode material.
Compared with the prior art, the invention adopts a simple chemical liquid phase method, H2PO2 −Partial hydrolysis of ions to produce OH−Ions, OH−Ions subsequently with unhydrolyzed H2PO2 −Ion production of pH by disproportionation3Molecule and HPO3 2−Ions. HPO3 2−The ions further react with Co2+Ions and OH−Ion reaction to produce Co11(HPO3)8(OH)6Seed crystal of Fe3+Incorporated into the crystal lattice. Adsorbed on Co11(HPO3)8(OH)6The isopropanol molecules on the seed passivate the surface atoms, rendering Co11(HPO3)8(OH)6And growing the seed crystal into 2D nano sheets. Fe doped Co11(HPO3)8(OH)6The nano-sheet array structure material shows excellent catalytic activity and stability for oxygen evolution reaction, hydrogen evolution reaction and full-water decomposition reaction, and the preparation process is environment-friendly, simple and low in cost.
Drawings
FIG. 1 shows Fe-doped Co prepared in example 111(HPO3)8(OH)6An X-ray powder diffraction (XRD) pattern of the nanosheet array structure material;
FIG. 2 shows Fe-doped Co prepared in example 111(HPO3)8(OH)6An energy dispersive X-ray spectroscopy (EDX) map of the nanosheet array structure material;
FIG. 3 shows Fe-doped Co prepared in example 111(HPO3)8(OH)6A Scanning Electron Microscope (SEM) image of the nanoplatelet array structure material;
FIG. 4 shows Fe-doped Co prepared in example 111(HPO3)8(OH)6A Transmission Electron Microscope (TEM) image of the nanosheet array structure material;
FIG. 5 shows Fe-doped Co prepared in example 111(HPO3)8(OH)6High resolution lattice fringe (HRTEM) images of nanoplate array structured materials;
FIG. 6 shows Fe-doped Co prepared in example 111(HPO3)8(OH)6A scanning electron microscope picture (SEM) and corresponding elemental distribution map of the nanosheet array structure material;
FIG. 7 shows Fe-doped Co prepared in example 111(HPO3)8(OH)6An infrared spectrogram of the nano-sheet array structure material;
FIG. 8 shows the Co doping with Fe in example 111(HPO3)8(OH)6A contact angle measurement result graph of the nano-sheet array structure material;
FIG. 9 shows Fe-doped Co amounts of 8.1% and 15.1% Fe prepared in example 211(HPO3)8(OH)6An X-ray powder diffraction (XRD) pattern of the nanosheet array structure material;
FIG. 10 shows Fe-doped Co amounts of 8.1% and 15.1% Fe prepared in example 211(HPO3)8(OH)6An energy dispersive X-ray spectroscopy (EDX) map of the nanosheet array structure material;
FIG. 11 shows Fe-doped Co with Fe doping amount of 8.1% prepared in example 211(HPO3)8(OH)6A Scanning Electron Microscope (SEM) image of the nanoplatelet array structure material;
FIG. 12 shows Fe-doped Co with 15.1% Fe doping amount prepared in example 211(HPO3)8(OH)6A Scanning Electron Microscope (SEM) image of the nanoplatelet array structure material;
FIG. 13 shows the Fe-doped Co with different Fe contents (8.1%, 11.7% and 15.1%) prepared in examples 1 and 211(HPO3)8(OH)6An LSV curve graph of Oxygen Evolution Reaction (OER) of the nanosheet array structure material;
FIG. 14 shows the Fe-doped Co with different Fe contents (8.1%, 11.7% and 15.1%) prepared in examples 1 and 211(HPO3)8(OH)6An LSV curve chart of Hydrogen Evolution Reaction (HER) of the nanosheet array structure material;
FIG. 15 shows the Co doping with Fe in example 311(HPO3)8(OH)6An LSV curve graph (an inset is a polarization curve under high current density) of the Oxygen Evolution Reaction (OER) of the nanosheet array structure material;
FIG. 16 shows the Co doping with Fe in example 311(HPO3)8(OH)6A current density time curve graph of the Oxygen Evolution Reaction (OER) of the nano-sheet array structure material;
FIG. 17 shows the Co doping of Fe in example 311(HPO3)8(OH)6A capacitance-current diagram of the nano-sheet array structure material at different scanning speeds;
FIG. 18 shows the Co doping with Fe in example 311(HPO3)8(OH)6Impedance plot of the nanosheet array structure material;
FIG. 19 shows the Co doping with Fe in example 411(HPO3)8(OH)6An LSV curve graph (an inset is a polarization curve under high current density) of the Hydrogen Evolution Reaction (HER) of the nanosheet array structure material;
FIG. 20 shows the doping of Fe with C in example 4o11(HPO3)8(OH)6A current density time curve diagram of Hydrogen Evolution Reaction (HER) of the nanosheet array structure material;
FIG. 21 shows the Co doping of Fe in example 611(HPO3)8(OH)6A polarization curve diagram of the total water decomposition of the nano-sheet array structure material in a two-electrode system (an inset is a polarization curve under high current density);
FIG. 22 shows the Co doping of Fe in example 611(HPO3)8(OH)6And (3) a current density time curve diagram of the total water decomposition of the nano-sheet array structure material in a two-electrode system.
Detailed Description
The invention is described in detail below with reference to the following examples and the accompanying drawings.
Example 1
Fe-doped Co11(HPO3)8(OH)6The preparation method of the nano-sheet array structure material comprises the following steps:
soaking foamed nickel with the size of 2 multiplied by 3 cm in 6M hydrochloric acid solution for 15 min, respectively washing the foamed nickel for 3 times by deionized water and absolute ethyl alcohol, and drying to obtain the foamed nickel with a clean surface. Accurately measuring 10 mL of deionized water and 30 mL of isopropanol, adding into a clean small beaker, and respectively weighing 0.6 mmol of Fe (NO)3)3·9H2O，1mmol Co(NO3)2·6H2O and 1mmol NaH2PO2·6H2Adding O into a small beaker, stirring and dissolving for 30 min to obtain a uniform solution. Transferring the solution to a 50 mL stainless steel reaction kettle with polytetrafluoroethylene as a lining, obliquely inserting the pretreated foamed nickel into the solution, sealing and reacting in a 160 ℃ oven for 6 hours, naturally cooling to room temperature after the reaction is finished, respectively cleaning the foamed nickel covering the sample for 3 times by using deionized water and absolute ethyl alcohol, and naturally drying the foamed nickel in an air atmosphere to obtain the Fe-doped Co11(HPO3)8(OH)6A nanosheet array structure material.
The product obtained in example 1 was subjected to X-ray powder diffractometryThe phase characterization was carried out, and the results are shown in FIG. 1, all diffraction peaks are similar to those of hexagonal phase Co in JCPDS No. 44-1326 card11(HPO3)8(OH)6And (5) performing anastomosis. The diffraction peaks were not shifted compared to the standard card number.
The product was analyzed using energy dispersive X-ray spectroscopy (EDX), as shown in fig. 2, with an atomic percentage of Fe, Co and P elements of 0.29:1:1.08, indicating successful coupling of Fe elements into the sample, from which an Fe doping level of 11.7% was calculated, with the nickel peak arising from the nickel foam substrate.
Morphological analysis of the sample prepared in example 1 was performed using a Scanning Electron Microscope (SEM), as shown in fig. 3, indicating that the sample consists of an array of nanosheets, the nanosheets having an average size of 300-500 nm.
The morphology of the sample was further observed using Transmission Electron Microscopy (TEM) and the results are shown in fig. 4, further indicating that the sample is composed of flexible nanoflakes.
High Resolution Transmission Electron Microscope (HRTEM) images of the nanoplatelets are shown in fig. 5, showing their crystalline nature, but also having some defects and distortions, indicating that the nanoplatelets have a rich defect structure. Wherein interplanar spacings of 0.37 nm and 0.42 nm correspond to Co, respectively11(HPO3)8(OH)6The (201) and (210) crystal planes of (a).
FIG. 6 is a SEM elemental distribution diagram illustrating Fe doped Co11(HPO3)8(OH)6Co, P, O and Fe elements in the nanosheet array structure material are uniformly distributed.
The IR spectrum of the product in FIG. 7 further confirms that Fe is doped with Co11(HPO3)8(OH)6The successful preparation. At 3442 cm−1The wide absorption band centered on the center is O-H stretching vibration at 2414 cm−1The absorption peak is P-H stretching vibration, 1639 cm−1The peak is P-O-H bending vibration, 1107, 1057 and 1016 cm−1The absorption peak is P-O stretching vibration, 573 cm−1The absorption peak at (a) is the bending vibration of the phosphite.
Using contact anglesMethod for respectively measuring Fe doped with Co11(HPO3)8(OH)6Surface wettability of the nanosheet structure. FIG. 8 shows the dropping of water droplets to Fe-doped Co11(HPO3)8(OH)6Typical water drop profile at the instant after the film surface. Fe doped Co11(HPO3)8(OH)6Contact angle of the film was about 9oIndicating the hydrophilicity of the product.
Example 2
Fe doped Co11(HPO3)8(OH)6The preparation method of the nano-sheet array structure material comprises the following steps:
accurately measuring 10 mL of deionized water and 30 mL of isopropanol, adding into a clean small beaker, and respectively weighing 0.4 mmol or 0.8mmol of Fe (NO)3)3·9H2O，1mmol Co(NO3)2·6H2O and 1mmol of NaH2PO2·6H2Adding O into a small beaker, and stirring uniformly. Obliquely inserting the dried foamed nickel into a stainless steel reaction kettle with a lining of 50 mL polytetrafluoroethylene, transferring the solution into the reaction kettle after the solution is fully dissolved, and reacting for 6 hours in an oven at 160 ℃ after sealing. After the reaction is completed, naturally cooling to room temperature, washing the foam nickel covering the sample for several times by using deionized water and absolute ethyl alcohol, and naturally drying the foam nickel covering the sample in an air atmosphere, wherein Fe (NO) is3)3·9H2When the addition amount of O is 0.4 mmol, Fe-doped Co consisting of nanosheets with Fe doping amount of 8.1% is obtained11(HPO3)8(OH)6A nanosheet array structure material; fe (NO)3)3·9H2When the addition amount of O is 0.8mmol, Fe-doped Co consisting of nanosheets with Fe doping amount of 15.1% is obtained11(HPO3)8(OH)6A nanosheet array structure material.
The product obtained in example 2 was subjected to phase characterization by X-ray powder diffractometer, and the results are shown in FIG. 9, in which all diffraction peaks are similar to those of hexagonal Co in JCPDS No. 44-1326 card11(HPO3)8(OH)6And (5) performing anastomosis.
The synthesized nanosheets were analyzed using energy dispersive X-ray spectroscopy (EDX), as shown in fig. 10, with the atomic percentages of Fe, Co, and P elements being 0.18:1:1.08 and 0.40:1:1.25, respectively, from which the Fe doping amounts were calculated to be 8.1% and 15.1%, with the nickel peaks originating from the nickel foam substrate.
The morphology of the sample prepared in example 2 was analyzed using a Scanning Electron Microscope (SEM), and fig. 11 and 12 are Fe-doped Co with Fe doping amounts of 8.1% and 15.1%, respectively11(HPO3)8(OH)6The SEM image of (a) shows that the samples are all array structures consisting of nanosheets.
Example 3
Fe-doped Co11(HPO3)8(OH)6The application of the nano-sheet structure material as an Oxygen Evolution Reaction (OER) catalyst.
The specific application method comprises the following steps: doping Fe with 0.5X 0.5cm area with Co11(HPO3)8(OH)6The nanosheet structure material was used as a working electrode, and a platinum wire and an Ag/AgCl electrode were used as a counter electrode and a reference electrode, respectively, for testing in a 1.0M KOH electrolyte solution using a CHI760E electrochemical workstation. Respectively with commercial RuO2And Co11(HPO3)8(OH)6Nanosheets loaded on foamed nickel as working electrodes, and their OER properties were measured separately as a comparison, Co11(HPO3)8(OH)6Based on example 1, Fe (NO) in the raw material is omitted3)3·9H2O is prepared. Linear Sweep Voltammetry (LSV) at 2.0 mV.s−1And the polarization curve was obtained at 90% ohmic compensation.
FIG. 13 is a Fe-doped Co with different Fe contents of 8.1%, 11.7% and 15.1%11(HPO3)8(OH)6Oxygen Evolution Reaction (OER) polarization curve of the nanoplatelets. It is shown that the doping amount of Fe significantly affects the OER activity, and the samples with the doping amount of Fe of 11.7% are better than those with the doping amounts of 8.1% and 15.1%.
FIG. 15 shows Fe doped with Co11(HPO3)8(OH)6Nano-sheet array structure material、Co11(HPO3)8(OH)6Nanosheet, RuO2Oxygen Evolution Reaction (OER) polarization curve with nickel foam, as can be seen from the figure, Fe doped Co11(HPO3)8(OH)6The nano-sheet structure material can realize 20 mA cm only by using the low overpotential of 206 mV−2Current density of (1) to Co11(HPO3)8(OH)6And commercial RuO2105 mV and 131mV smaller.
In addition, Fe is doped with Co11(HPO3)8(OH)6The nano-sheet structure material can reach 200 mA cm under smaller overpotentials of 252 mV and 268 mV−2And 500 mA · cm−2The large current density of (2) in fig. 16 is a graph of current density versus time under overpotentials 206, 252, 268 mV, and it can be seen that the current density is maintained to be above the initial 98.5% after 12 hours of continuous electrolytic reaction, showing excellent electrocatalytic stability.
FIG. 17 is a plot of capacitance current at different sweep rates, evaluating electrochemically active area of material using double layer capacitance, Fe doped Co11(HPO3)8(OH)6The electric double layer capacitance was 4.95 mF. cm−2Is greater than Co11(HPO3)8(OH)62.45 mF. cm−2Indicating that the doping of Fe increases the electrochemically active area of the sample.
FIG. 18 is an Electrochemical Impedance (EIS) diagram showing Fe doped Co11(HPO3)8(OH)6The semicircular diameter of the nanosheet array structure material is small, which shows that the nanosheet array structure material is small in resistance and has quicker catalytic kinetics; and the slope of the straight line part is large, which shows better quality transmission behavior.
Example 4
Fe-doped Co11(HPO3)8(OH)6Application of the nano-sheet structure material as a Hydrogen Evolution Reaction (HER) catalyst.
The specific application method comprises the following steps: doping Fe with 0.5X 0.5cm area with Co11(HPO3)8(OH)6The nanosheet structure material was used as a working electrode, a carbon rod and an Ag/AgCl electrode were used as a counter electrode and a reference electrode, respectively, and the test was performed in a 1.0M KOH electrolyte solution using a CHI760E electrochemical workstation. Respectively as commercial Pt/C and Co11(HPO3)8(OH)6Nanosheets loaded on foamed nickel as working electrodes, their HER properties were measured separately as a comparison, Co11(HPO3)8(OH)6Is prepared by omitting Fe (NO) from the raw material based on example 13)3·9H2O is prepared. Linear Sweep Voltammetry (LSV) at 2.0 mV · s−2And the polarization curve was obtained at 90% ohmic compensation.
FIG. 14 is a Fe-doped Co with different Fe contents of 8.1%, 11.7% and 15.1%11(HPO3)8(OH)6Hydrogen Evolution Reaction (HER) polarization curve of the nanoplatelets. The doping amount of Fe also significantly influences the HER activity of the catalyst, and the sample with the doping amount of Fe of 11.7% achieves the best.
FIG. 19 shows Fe doped with Co11(HPO3)8(OH)6Nanosheet array structure material, Co11(HPO3)8(OH)6Hydrogen Evolution Reaction (HER) polarization curves of nanosheets, Pt/C and foamed nickel, as can be seen from the figure, Fe doped Co11(HPO3)8(OH)6The nano-sheet structure can reach 10 mA cm under the overpotential of 102 mV−2Current density much less than that of Co11(HPO3)8(OH)6189 mV of catalyst. Although Pt/C electrodes show outstanding HER activity at low current densities, at high current densities the material is very prone to flaking off and activity is affected.
In addition, Fe is doped with Co11(HPO3)8(OH)6The nanosheet structure can reach 200 mA-cm under the relatively small overpotentials of 228 mV and 263 mV−2And 500 mA · cm−2The current density of (2). HER electrocatalytic stability was evaluated using a current density time curve at constant overpotential 138, 228, 263 mV, as shown in figure 20, over a 12 hour continuous electrolysis reactionThe flow density was maintained above the initial 96.4% and good HER electrocatalytic stability was exhibited.
Example 6
Fe-doped Co11(HPO3)8(OH)6The application of the nano-sheet structure material as a catalyst for the total-moisture decomposition reaction.
The specific application method comprises the following steps: 2 Fe areas of 0.5X 0.5cm were doped with Co11(HPO3)8(OH)6The nanosheet structure was assembled as an anode and cathode, respectively, in a two-electrode electrolytic cell and tested for full water splitting performance in a 1.0M KOH electrolyte solution. And with RuO2And Pt/C as the anode and cathode composition of the electric couple for comparison.
Fig. 21, 22 are the 90% iR compensated LSV polarization curve and the current density time curve at constant voltage, respectively. As can be seen from FIG. 21, Fe is doped with Co11(HPO3)8(OH)6The nano-sheet array structure material can reach 10 mA cm under the voltage of 1.494V−2The current density is only 1.772V required to drive 500 mA cm−2High current density. Despite the commercial RuO2The electric couple composed of Pt and C has slightly high activity under low current density, but can not reach 500 mA cm because the material is easy to fall off−2High current density.
As can be seen from FIG. 22, Fe is doped with Co11(HPO3)8(OH)6The nanosheet array structure material does not undergo obvious attenuation after being continuously electrolyzed at constant voltage of 1.530, 1.690 and 1.772V for 12 hours, and the current density is kept to be more than the initial 97.1 percent, which shows that the nanosheet array structure material has excellent durability in a double-electrode electrolytic cell.
The above detailed description of the Fe-doped cobalt hydroxyphosphite nanosheet array structure material and the preparation method and application thereof with reference to the examples is illustrative and not restrictive, and several examples can be cited according to the limited scope, so that changes and modifications that do not depart from the general concept of the present invention shall fall within the protection scope of the present invention.
Claims (7)
1. Fe-doped Co11(HPO3)8(OH)6The preparation method of the nano-sheet array structure material is characterized by comprising the following steps:
dissolving iron salt, cobalt salt and hypophosphite in a mixed solvent of water and isopropanol, transferring the solution to a reaction kettle, obliquely placing foamed nickel in the solution, carrying out solvothermal reaction, cooling to room temperature after the reaction is finished, washing and drying a product to obtain the Fe-doped Co11(HPO3)8(OH)6A nanosheet array structure material;
the mass ratio of the ferric salt to the cobalt salt to the hypophosphite is 0.2-0.8: 1-2: 1;
the volume ratio of the water to the isopropanol is 1-2: 3-2;
the solvent thermal reaction condition is that the reaction is carried out for 4 to 8 hours at 160 ℃.
2. The method of claim 1, wherein the iron salt is ferric nitrate nonahydrate; the cobalt salt is cobalt nitrate hexahydrate; the hypophosphite is sodium hypophosphite.
3. The production method according to claim 1 or 2, wherein the concentration of the hypophosphite is 0.025M in the mixed solvent of water and isopropyl alcohol.
4. A Fe-doped Co prepared by the method of any one of claims 1 to 311(HPO3)8(OH)6A nanosheet array structure material.
5. Fe doped Co of claim 411(HPO3)8(OH)6The application of the nano-sheet array structure material as an Oxygen Evolution Reaction (OER) electrocatalyst.
6. Fe-doped Co according to claim 411(HPO3)8(OH)6Nano-sheetApplication of array structure material as Hydrogen Evolution Reaction (HER) electrocatalyst.
7. Fe-doped Co according to claim 411(HPO3)8(OH)6The application of the nano-sheet array structure material as an all-water decomposition reaction electrocatalyst.
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| CN113174608B (en) * | 2021-03-02 | 2022-10-25 | 江苏大学 | Preparation method of double-doped porous cobalt phosphide nanosheet electrocatalytic material |
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