CN110975914A - Phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material and preparation method and application thereof - Google Patents
Phosphorus-doped nickel iron oxide 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 65
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- DMTIXTXDJGWVCO-UHFFFAOYSA-N iron(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Fe++].[Ni++] DMTIXTXDJGWVCO-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000000137 annealing Methods 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- 239000002135 nanosheet Substances 0.000 claims abstract description 4
- 239000000969 carrier Substances 0.000 claims abstract description 3
- 238000011065 in-situ storage Methods 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 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 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 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 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- HMDDNMYOIJFMET-UHFFFAOYSA-N N.[O-2].[Fe+2].[Ni+2] Chemical compound N.[O-2].[Fe+2].[Ni+2] HMDDNMYOIJFMET-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052573 porcelain Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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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
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
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- B01J35/58—
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- B01J35/61—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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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 nickel iron oxide nitrogen-doped carbon nanofiber composite material which is characterized in that the phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material is prepared by growing NiFe-LDH nanosheets in situ on the surface of nitrogen-doped carbon nanofibers by taking the nitrogen-doped carbon nanofibers as carriers. The preparation method comprises two processes of annealing process and high-temperature phosphorus doping. The phosphorus-doped nickel 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 nickel iron oxide nitrogen-doped carbon nanofiber composite material and a preparation method and application thereof.
Background
Oxygen evolution reactions have been of direct interest as one of the key processes for many energy related applications. However, the high reaction energy barrier and the electronic mechanism determine the high reaction overpotential and the slow reaction rate, so that the oxygen evolution reaction is the rate-limiting reaction in the water decomposition process. Therefore, in practical applications, a highly efficient and stable catalyst capable of reducing the overpotential of the reaction and accelerating the reaction is required. In practical application, the noble metal-based Ru, Ir and oxide catalysts thereof are widely applied, but the characteristics of high price and poor cycle stability make the noble metal-based Ru, Ir and oxide catalysts thereof unable to meet the increasing environmental and energy requirements. Therefore, it is necessary to explore alternative cheap, efficient and stable OER catalysts. At present, the OER catalyst of transition metal (nickel, iron, cobalt, etc.) compound is continuously paid attention and researched by researchers, wherein the oxide/hydroxide has higher OER activity, and researches find that the mixed transition metal compound has higher OER catalytic performance compared with a single transition metal compound, wherein the nickel iron oxide is found to have quite excellent catalytic performance in alkaline electrolyte.
The catalytic activity of the catalyst depends mainly on its electronic state and surface area, and non-metallic heteroatom doping is considered to be an effective method for optimizing the catalytic performance. Wherein, the phosphorus atom has higher electron donating ability, and the electrochemical performance can be further improved by adjusting the electronic structure of the catalyst.
Disclosure of Invention
The invention aims to provide a phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material as well as a preparation method and application thereof.
In order to achieve the purpose, the invention provides a phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material which is characterized in that the phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material is prepared by growing NiFe-LDH nanosheets in situ on nitrogen-doped carbon nanofibers by taking the nitrogen-doped carbon nanofibers as carriers.
The invention also provides a preparation method of the phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material, which is characterized by comprising the following steps of:
step 1: dissolving nickel nitrate hexahydrate, ferric nitrate nonahydrate and ammonium fluoride in deionized water, and performing ultrasonic treatment for 5-20min to uniformly disperse the nickel 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 ultrasonic treatment for 1-3 hours, then carrying out hydrothermal reaction at the temperature of 80-140 ℃ for 6-12 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 10-14 hours 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 2-6 ℃/min for 1-3h to obtain the nickel iron oxide nitrogen-doped carbon nanofiber composite material;
and 4, step 4: mixing the nickel-iron-oxide-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 2-6 ℃/min, and the time is 1-3h, so that the phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material is obtained.
Preferably, in the step 1, the molar ratio of the nickel nitrate hexahydrate, the ferric nitrate nonahydrate and the ammonium fluoride is (1-3): 1-5): 8-12, and the concentration of the nickel nitrate hexahydrate in the solution A is 0.0125-0.0375 mol/L.
More preferably, in the step 1, the molar ratio of the nickel 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 nickel iron oxide nitrogen is doped with the carbon nanofiber composite material and NaH2PO2·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 nickel iron oxide nitrogen-doped carbon nanofiber composite material as an OER catalyst.
The nickel 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 nickel iron oxide is avoided, the active surface area of the nickel iron oxide is greatly increased, and the composite material has the advantages of large specific surface area, good conductivity, stable physical and chemical 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 nickel iron oxide, improves the catalytic performance of the nickel iron oxide by changing the charge distribution of the eigen state of the nickel iron oxide, and is a simple and efficient modification method.
2. The nitrogen-doped carbon nanofiber is used as a substrate, and the nickel iron oxide nanosheets are uniformly grown on the surface of the substrate, so that the problem of easy agglomeration in the synthesis process of the nickel iron oxide is avoided, and the active surface area of the nickel iron oxide is greatly increased.
3. The phosphorus-doped nickel 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 of the preparation of the phosphorus doped nickel iron oxide nitrogen doped carbon nanofiber composite material of the present invention.
Fig. 2 is an XRD spectrum of the phosphorus doped nickel iron oxide nitrogen doped carbon nanofiber composite in example 1 of the present invention.
Fig. 3 is an SEM image of the phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite in example 1 of the present invention.
Fig. 4 is an OER performance graph obtained by using the phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite obtained in example 1 of the present invention as a catalyst for an OER reaction. a is the OER polarization curve of the phosphorus doped nickel 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 nickel iron oxide nitrogen-doped carbon nanofiber composite material, which includes the following specific steps:
step 1: dissolving nickel nitrate hexahydrate, ferric nitrate nonahydrate and ammonium fluoride in deionized water according to the molar ratio of 1:2:5, and performing ultrasonic treatment for 10min to uniformly disperse the nickel 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 treatment for 1 hour, transferring the solution A into a hydrothermal kettle for hydrothermal reaction at the reaction temperature of 120 ℃ for 10 hours, cooling the solution A to room temperature after the reaction is finished, washing the sample with a mixed solution of ethanol and water, and drying the sample 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 as to obtain the nickel iron oxide nitrogen-doped carbon nanofiber composite material;
and 4, step 4: mixing the nickel-iron-oxide-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 2h, so that the phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material is obtained.
Example 2
As shown in fig. 1, this embodiment provides a method for preparing a phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material, which includes the following specific steps:
step 1: dissolving nickel 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 nickel 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 treatment for 1 hour, transferring the solution A into a hydrothermal kettle for hydrothermal reaction at the reaction temperature of 120 ℃ for 10 hours, cooling the solution A to room temperature after the reaction is finished, washing the sample with a mixed solution of ethanol and water, and drying the sample 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 as to obtain the nickel iron oxide nitrogen-doped carbon nanofiber composite material;
and 4, step 4: mixing the nickel-iron-oxide-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 2h, so that the phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material is obtained.
The structure and performance of the phosphorus-doped nickel iron oxide 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 nife-doped carbon nanofiber composite showed distinct 6 diffraction patterns at 18.8 °, 31.3 °, 37.2 °, 44.1 °, 58.7 ° and 64.1 °, corresponding to the (111), (220), (311), (400), (511) and (440) diffraction planes of nife. The result of the XRD spectrum shows that the phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material obtained in the experiment is compounded by nickel 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 phosphorus-doped nickel iron oxide is uniformly coated on the nitrogen-doped carbon nanofibers, thereby avoiding the agglomeration of the nickel iron oxide.
(4) The electrochemical workstation test results show that: the OER polarization curve of the phosphorus doped nickel iron oxide nitrogen doped carbon nanofiber composite catalyst clearly shows its excellent OER activity. For the phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material, the thickness is 10mA cm-2The overpotential of (2) is 278mV at the current density of (3). The Tafel diagram of the corresponding catalyst shows that the phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite catalyst has 51.7mV dec-1The Tafel slope shows that the phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material has better catalytic activity when being used as an OER catalyst.
In conclusion, the phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material is prepared based on the strategy that phosphorus-doped nickel iron oxide is combined with nitrogen-doped carbon nanofiber 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 nickel iron oxide and improves the conductivity, so that the material shows excellent OER catalytic activity.
Claims (9)
1. The phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material is characterized by being prepared by taking nitrogen-doped carbon nanofibers as carriers and growing NiFe-LDH nanosheets in situ on the nitrogen-doped carbon nanofibers.
2. The method for preparing the phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material as claimed in claim 1, characterized by comprising the following steps:
step 1: dissolving nickel nitrate hexahydrate, ferric nitrate nonahydrate and ammonium fluoride in deionized water, and performing ultrasonic treatment for 5-20min to uniformly disperse the nickel 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 ultrasonic treatment for 1-3 hours, then carrying out hydrothermal reaction at the temperature of 80-140 ℃ for 6-12 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 10-14 hours 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 2-6 ℃/min for 1-3h to obtain the nickel iron oxide nitrogen-doped carbon nanofiber composite material;
and 4, step 4: mixing the nickel-iron-oxide-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 2-6 ℃/min, and the time is 1-3h, so that the phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material is obtained.
3. The method for preparing the phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material as claimed in claim 2, wherein in the step 1, the molar ratio of nickel nitrate hexahydrate, ferric nitrate nonahydrate and ammonium fluoride is (1-3) to (1-5) to (8-12), and the concentration of nickel nitrate hexahydrate in the solution A is 0.0125-0.0375 mol/L.
4. The method for preparing the phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material as claimed in claim 3, wherein in the step 1, the molar ratio of nickel nitrate hexahydrate, ferric nitrate nonahydrate and ammonium fluoride is 1:2: 10.
5. The method for preparing the phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material as claimed in claim 2, wherein in the step 2, the hydrothermal reaction temperature is 120 ℃, the reaction time is 10 hours, and the drying time is 12 hours.
6. The method for preparing the phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material as claimed in claim 2, 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.
7. The method of making a phosphorus doped nickel iron oxide nitrogen doped carbon nanofiber composite as claimed in claim 2, wherein in step 4, the nickel iron oxide nitrogen doped carbon nanofiber composite and NaH2PO2·H2The mass ratio of O is 1: 5.
8. The method for preparing the phosphorus-doped nickel iron oxide nitrogen-doped carbon nanofiber composite material as claimed in claim 2, 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.
9. Use of the phosphorus doped nickel iron oxide nitrogen doped carbon nanofiber composite of claim 1 as an OER catalyst.
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Cited By (4)
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|---|---|---|---|---|
| CN111710533A (en) * | 2020-06-28 | 2020-09-25 | 南京工业大学 | Graphene porous membrane loaded with layered double hydroxide and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111710533A (en) * | 2020-06-28 | 2020-09-25 | 南京工业大学 | Graphene porous membrane loaded with layered double hydroxide and preparation method and application thereof |
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| WO2023010709A1 (en) * | 2021-08-03 | 2023-02-09 | 中国科学院青岛生物能源与过程研究所 | Phosphorus-doped nickel aluminum oxide, and preparation method therefor and use thereof |
| CN113745530A (en) * | 2021-09-08 | 2021-12-03 | 山东大学 | High-performance spherical phosphorus-doped nickel oxide lithium carbon dioxide battery positive electrode catalytic material and preparation method thereof |
| CN113745530B (en) * | 2021-09-08 | 2023-02-28 | 山东大学 | High-performance spherical phosphorus-doped nickel oxide lithium carbon dioxide battery positive electrode catalytic material and preparation method thereof |
| CN115440508A (en) * | 2022-08-25 | 2022-12-06 | 信阳师范学院 | Preparation method of array type nickel-iron-nitrogen nanosheet for supercapacitor |
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