CN110813361B - Phosphorus-doped cobalt oxide iron nitrogen-doped carbon nanofiber composite material and preparation method and application thereof - Google Patents
Phosphorus-doped cobalt oxide iron nitrogen-doped carbon nanofiber composite material and preparation method and application thereof Download PDFInfo
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- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 59
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- PCIREHBGYFWXKH-UHFFFAOYSA-N iron oxocobalt Chemical compound [Fe].[Co]=O PCIREHBGYFWXKH-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- QRXDDLFGCDQOTA-UHFFFAOYSA-N cobalt(2+) iron(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Co+2].[O-2] QRXDDLFGCDQOTA-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000000137 annealing Methods 0.000 claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- 239000000969 carrier Substances 0.000 claims abstract 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 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 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 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound 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 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 7
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims description 3
- TUJODQMHDVXSJH-UHFFFAOYSA-N [N].[Fe].[Co]=O Chemical compound [N].[Fe].[Co]=O TUJODQMHDVXSJH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229940031182 nanoparticles iron oxide Drugs 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- MCONQMQZJCTYCP-UHFFFAOYSA-N [N].[Fe].[Co] Chemical compound [N].[Fe].[Co] MCONQMQZJCTYCP-UHFFFAOYSA-N 0.000 claims 2
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical class [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- B01J35/33—
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/397—
-
- B01J35/58—
-
- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- 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 phosphorus-doped cobalt oxide iron nitrogen-doped carbon nanofiber composite material which is characterized by being prepared by taking nitrogen-doped carbon nanofibers as carriers and growing CoFe-LDH nanoparticles on the surfaces of the nitrogen-doped carbon nanofibers in situ. The preparation method comprises two processes of annealing process and high-temperature phosphorus doping. The phosphorus-doped cobalt iron oxide nitrogen-doped carbon nanofiber composite material prepared by the invention has the advantages of large specific surface area, good conductivity, stable physical and chemical properties, excellent electrochemical performance and the like.
Description
Technical Field
The invention belongs to the technical field of metal oxide-carbon materials, and particularly relates to a phosphorus-doped cobalt oxide iron nitrogen-doped carbon nanofiber composite material and a preparation method and application thereof.
Background
With the increasing consumption of fossil fuels in human society, the use of renewable and clean energy is the key to solving such problems, and the production of renewable and clean energy by electrochemical decomposition of water is an important approach. Oxygen evolution reaction is one of the key processes for electrochemically decomposing water due to its inherent advantageFor slow kinetic reaction processes, large overpotentials are required, which creates a huge energy consumption problem. Therefore, research on an inexpensive and efficient OER catalyst with excellent cycle performance is urgently needed to reduce the reaction energy barrier and accelerate the reaction efficiency. At present, to replace the commonly used noble metal catalyst RuO2And IrO2Etc., transition metals such as iron, cobalt, nickel hydroxides/oxides and mixed metal oxides thereof have been continuously studied, and they have been proved to have extremely high oxygen evolution catalytic activity.
Among them, the drill-based catalysts are receiving wide attention due to their relatively abundant reserves and oxygen evolution catalytic activities comparable to noble metal oxides. As the oxygen evolution catalyst, the catalyst not only has lower oxygen evolution overpotential and IrO2-Has similar overpotential and much better cycling stability than IrO2Thus, the material is expected to be an excellent electro-catalytic material. At present, researchers mainly improve the active surface area of a catalyst and the conductivity of the catalyst by regulating and controlling a nano structure, doping of heteroatoms, compounding with a carbon material and the like, so that the material has high catalytic activity and efficiency. The defects can be introduced by doping the heteroatom, so that the ion channel of the metal oxide semiconductor is enlarged, the conductive capability is enhanced, and the conductivity is further improved. And the hetero atoms doped on the surface of the material can change the structural characteristics and surface chemical properties of the material, so that the electronic structure of the material is regulated and controlled, and the electronic conductivity is improved.
Disclosure of Invention
The invention aims to provide a phosphorus-doped cobalt oxide iron nitrogen-doped carbon nanofiber composite material and a preparation method thereof.
In order to achieve the above object, the present invention provides a phosphorus-doped cobalt iron oxide nitrogen-doped carbon nanofiber composite material, which is characterized in that the phosphorus-doped cobalt iron oxide nitrogen-doped carbon nanofiber composite material is prepared by growing phosphorus-doped cobalt iron oxide nanoparticles in situ on the surface of a nitrogen-doped carbon nanofiber by using a nitrogen-doped carbon nanofiber as a carrier.
The invention also provides a preparation method of the phosphorus-doped cobalt oxide iron nitrogen-doped carbon nanofiber composite material, which is characterized by comprising the following steps of:
step 1: dissolving cobalt nitrate hexahydrate, ferric nitrate nonahydrate and ammonium fluoride in deionized water, and performing ultrasonic treatment for 10-40min to uniformly disperse the cobalt nitrate hexahydrate, the ferric nitrate nonahydrate and the ammonium fluoride to obtain a solution A;
step 2: adding nitrogen-doped carbon nanofibers into the solution A prepared in the step 1, carrying out hydrothermal reaction at the temperature of 80-140 ℃ for 6-12h, cooling to room temperature after the reaction is finished, washing a sample by using a mixed solution of ethanol and water, and drying at the temperature of 80 ℃ for 10-14h to obtain a precursor;
and step 3: annealing the precursor prepared in the step 2 at the temperature of 250-450 ℃ in a non-oxidizing atmosphere at the heating rate of 2-8 ℃/min for 1-3h to obtain the cobalt oxide-iron nitrogen doped carbon nanofiber composite material;
and 4, step 4: mixing the cobalt oxide, iron and nitrogen doped carbon nanofiber composite material prepared in the step 3 and NaH2PO2·H2And O is put in a porcelain boat according to the mass ratio of 1 (2-10), annealing treatment is carried out in a non-oxidizing atmosphere at the temperature of 250-450 ℃, the heating rate is 2-8 ℃/min, and the time is 1-3h, so that the phosphorus-doped cobalt oxide iron nitrogen-doped carbon nanofiber composite material is obtained.
Preferably, in the step 1, the molar ratio of the cobalt nitrate hexahydrate, the ferric nitrate nonahydrate and the ammonium fluoride is (1-3): 1-5): 8-12, and the concentration of the cobalt nitrate hexahydrate in the solution A is 0.0125-0.0375 mol/L.
More preferably, in the step 1, the molar ratio of the cobalt nitrate hexahydrate, the ferric nitrate nonahydrate and the ammonium fluoride is 1:2: 10.
Preferably, in the step 2, the hydrothermal reaction temperature is 120 ℃ and the reaction time is 10 h.
Preferably, in the step 2, the drying time is 12 h.
Preferably, in the step 3, the annealing temperature is 350 ℃, the heating rate is 5 ℃/min, the processing time is 2h, and the non-oxidizing atmosphere is nitrogen.
Preferably, in the step 4, the cobalt oxide, iron and nitrogen doped carbon nanofiber composite material and NaH are adopted2PO2·H2The mass ratio of O is 1: 5.
Preferably, in the step 4, the annealing temperature is 350 ℃, the heating rate is 5 ℃/min, the processing time is 2h, and the non-oxidizing atmosphere is nitrogen.
The invention also provides application of the phosphorus-doped cobalt oxide iron nitrogen-doped carbon nanofiber composite material as an OER catalyst.
The cobalt iron oxide in the composite material prepared by the invention uniformly grows on the surface of the nitrogen-doped carbon nanofiber, so that the problem of easy agglomeration in the synthesis process of the cobalt iron oxide is avoided, the active surface area of the cobalt iron oxide is greatly increased, and the composite material has the advantages of large specific surface area, good conductivity, stable physicochemical properties, excellent electrochemical performance and the like.
Compared with the prior art, the invention has the following remarkable advantages:
1. the invention dopes phosphorus element in the conventional cobalt iron oxide, improves the catalytic performance of the cobalt iron oxide by changing the charge distribution of the eigen state of the cobalt iron oxide, and is a simple and efficient modification method.
2. The nitrogen-doped carbon nanofiber is used as a substrate, and cobalt iron oxide nanoparticles are uniformly grown on the surface of the substrate, so that the problem of easy agglomeration in the synthesis process of cobalt iron oxide is avoided, and the active surface area of the cobalt iron oxide is greatly increased.
3. The phosphorus-doped cobalt iron oxide nitrogen-doped carbon nanofiber composite material prepared by the invention has the advantages of large specific surface area, good conductivity, stable physical and chemical properties, excellent electrochemical performance and the like.
Drawings
FIG. 1 is a flow chart illustrating the preparation of a phosphorus-doped cobalt iron oxide nitrogen-doped carbon nanofiber composite in example 1 of the present invention;
FIG. 2 is an XRD spectrum of the phosphorus-doped cobalt oxide iron nitrogen-doped carbon nanofiber composite material in example 1 of the present invention;
FIG. 3 is an SEM image of a phosphorus-doped cobalt iron oxide nitrogen-doped carbon nanofiber composite in example 1 of the present invention;
FIG. 4 is an OER performance map obtained by using the phosphorus-doped cobalt oxide iron nitrogen-doped carbon nanofiber composite material obtained in the invention as a catalyst for OER reaction; a is the OER polarization curve of the phosphorus-doped cobalt iron oxide nitrogen-doped carbon nanofiber composite obtained in example 1, and b is the corresponding Tafel curve.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
As shown in fig. 1, this embodiment provides a method for preparing a phosphorus-doped cobalt oxide iron nitrogen-doped carbon nanofiber composite material, which includes the following specific steps:
step 1: dissolving cobalt nitrate hexahydrate, ferric nitrate nonahydrate and ammonium fluoride in deionized water according to the molar ratio of 1:2:10, and performing ultrasonic treatment for 10min to uniformly disperse the cobalt nitrate hexahydrate, the ferric nitrate nonahydrate and the ammonium fluoride to obtain a solution A;
step 2: adding nitrogen-doped carbon nanofibers into the solution A prepared in the step 1, performing ultrasonic dispersion for 1 hour, performing hydrothermal reaction at the reaction temperature of 120 ℃ for 10 hours, cooling to room temperature after the reaction is finished, washing a sample by using a mixed solution of ethanol and water, and drying at the temperature of 80 ℃ for 12 hours to obtain a precursor;
and step 3: annealing the precursor prepared in the step 2 at 350 ℃ in a nitrogen atmosphere, wherein the heating rate is 5 ℃/min, and the time is 2h, so that the cobalt oxide iron nitrogen-doped carbon nanofiber composite material is obtained;
and 4, step 4: mixing the cobalt oxide, iron and nitrogen doped carbon nanofiber composite material prepared in the step 3 and NaH2PO2·H2And O is put in a porcelain boat according to the mass ratio of 1:5, annealing treatment is carried out in nitrogen atmosphere at 350 ℃, the heating rate is 5 ℃/min, and the time is 1-3h, so that the phosphorus-doped cobalt iron oxide nitrogen-doped carbon nanofiber composite material is obtained.
The structure and performance of the phosphorus-doped cobalt oxide iron nitrogen-doped carbon nanofiber composite material obtained by the invention are characterized and tested by using X-ray diffraction (XRD), a Scanning Electron Microscope (SEM) and an electrochemical workstation, and the results are as follows:
(1) XRD test results show that: as shown in fig. 2, the XRD curves of the phosphorus-doped cobalt iron oxide nitrogen-doped carbon nanofiber composite material show 5 distinct diffraction patterns at 19.4 °, 30.3 °, 35.6 °, 54.1 ° and 57.4 °, which correspond to the (111), (220), (311), (442) and (511) diffraction crystal planes of cobalt iron oxide, respectively. The result of the XRD spectrum shows that the phosphorus-doped cobalt iron oxide nitrogen-doped carbon nanofiber composite material obtained in the experiment is compounded by cobalt iron oxide and nitrogen-doped carbon, which directly illustrates that the preparation method provided by the present invention is feasible and is shown in fig. 1.
(2) The SEM test results show that: as shown in fig. 3, the nitrogen-doped carbon nanofibers are uniformly coated with the phosphorus-doped cobalt iron oxide, thereby avoiding the agglomeration of the cobalt iron oxide.
(4) The electrochemical workstation test results show that: the OER polarization curve of the phosphorus doped cobalt oxide iron nitrogen doped carbon nanofiber composite catalyst clearly shows its excellent OER activity. For the phosphorus-doped cobalt oxide iron nitrogen-doped carbon nanofiber composite material, the concentration is 10mA cm-2The overpotential of (3) is 311 mV at the current density of (3). The Tafel diagram of the corresponding catalyst shows that the phosphorus-doped cobalt oxide iron nitrogen-doped carbon nanofiber composite catalyst has 60mV dec-1The Tafel slope shows that the phosphorus-doped cobalt oxide iron nitrogen-doped carbon nanofiber composite material has better catalytic activity when being used as an OER catalyst.
In conclusion, the phosphorus-doped cobalt iron oxide nitrogen-doped carbon nanofiber composite material is prepared based on a strategy that phosphorus-doped cobalt iron oxide is combined with nitrogen-doped carbon nanofibers to serve as a substrate, and the design of heteroatom doping obviously improves the OER catalytic activity of the catalyst. Meanwhile, the carbon nanofiber doped with nitrogen as the substrate avoids the agglomeration phenomenon of cobalt iron oxide and improves the conductivity, so that the material shows excellent OER catalytic activity.
Claims (8)
1. A preparation method of a phosphorus-doped cobalt oxide iron nitrogen-doped carbon nanofiber composite material is characterized by comprising the following steps of:
step 1: dissolving cobalt nitrate hexahydrate, ferric nitrate nonahydrate and ammonium fluoride in deionized water, and performing ultrasonic treatment for 10-40min to uniformly disperse the cobalt nitrate hexahydrate, the ferric nitrate nonahydrate and the ammonium fluoride to obtain a solution A;
step 2: adding nitrogen-doped carbon nanofibers into the solution A prepared in the step 1, carrying out hydrothermal reaction at the temperature of 80-140 ℃ for 6-12h, cooling to room temperature after the reaction is finished, washing a sample by using a mixed solution of ethanol and water, and drying at the temperature of 80 ℃ for 10-14h to obtain a precursor;
and step 3: annealing the precursor prepared in the step 2 at the temperature of 250-450 ℃ in a non-oxidizing atmosphere at the heating rate of 2-8 ℃/min for 1-3h to obtain the cobalt oxide-iron nitrogen doped carbon nanofiber composite material;
and 4, step 4: mixing the cobalt oxide, iron and nitrogen doped carbon nanofiber composite material prepared in the step 3 and NaH2PO2·H2Placing O in a porcelain boat according to the mass ratio of 1 (2-10), and annealing at the temperature of 250-450 ℃ in a non-oxidizing atmosphere at the heating rate of 2-8 ℃/min for 1-3h to obtain the phosphorus-doped cobalt oxide iron nitrogen-doped carbon nanofiber composite material;
the phosphorus-doped cobalt iron oxide nitrogen-doped carbon nanofiber composite material is prepared by taking nitrogen-doped carbon nanofibers as carriers and growing phosphorus-doped cobalt iron oxide nanoparticles in situ on the surfaces of the nitrogen-doped carbon nanofibers.
2. The method for preparing the phosphorus-doped cobalt oxide-iron nitrogen-doped carbon nanofiber composite material as claimed in claim 1, wherein in the step 1, the molar ratio of the cobalt nitrate hexahydrate, the iron nitrate nonahydrate and the ammonium fluoride is (1-3): 1-5): 8-12, and the concentration of the cobalt nitrate hexahydrate in the solution A is 0.0125-0.0375 mol/L.
3. The method for preparing the phosphorus-doped cobalt oxide-iron nitrogen-doped carbon nanofiber composite material as claimed in claim 2, wherein in the step 1, the molar ratio of cobalt nitrate hexahydrate, iron nitrate nonahydrate and ammonium fluoride is 1:2: 10.
4. The method for preparing the phosphorus-doped cobalt oxide, iron and nitrogen-doped carbon nanofiber composite material as claimed in claim 1, wherein in the step 2, the hydrothermal reaction temperature is 120 ℃, the reaction time is 10 hours, and the drying time is 12 hours.
5. The method for preparing the phosphorus-doped cobalt oxide, iron and nitrogen-doped carbon nanofiber composite material as claimed in claim 1, wherein in the step 3, the annealing treatment temperature is 350 ℃, the heating rate is 5 ℃/min, the treatment time is 2h, and the non-oxidizing atmosphere is nitrogen.
6. The method of claim 1, wherein in step 4, the CoFeNx-doped carbon nanofiber composite and NaH are mixed2PO2·H2The mass ratio of O is 1: 5.
7. The method for preparing the phosphorus-doped cobalt oxide, iron and nitrogen-doped carbon nanofiber composite material as claimed in claim 1, wherein in the step 4, the annealing treatment temperature is 350 ℃, the heating rate is 5 ℃/min, the treatment time is 2h, and the non-oxidizing atmosphere is nitrogen.
8. The use of the phosphorus-doped cobalt iron nitrogen oxide-doped carbon nanofiber composite prepared by the method for preparing a phosphorus-doped cobalt iron nitrogen oxide-doped carbon nanofiber composite as claimed in claim 2 as an OER catalyst.
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