CN114990621A - Surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material and preparation method and application thereof - Google Patents
Surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 71
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- DSMZRNNAYQIMOM-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe].[Mo] DSMZRNNAYQIMOM-UHFFFAOYSA-N 0.000 title claims abstract 15
- 239000002243 precursor Substances 0.000 claims abstract description 51
- 150000004767 nitrides Chemical class 0.000 claims abstract description 28
- 238000000137 annealing Methods 0.000 claims abstract description 22
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- 238000003786 synthesis reaction Methods 0.000 claims abstract description 14
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- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
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- 229960002089 ferrous chloride Drugs 0.000 claims description 12
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 12
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- KWUUWVQMAVOYKS-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe][Mo][Mo] KWUUWVQMAVOYKS-UHFFFAOYSA-N 0.000 description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 239000000843 powder Substances 0.000 description 15
- 239000002244 precipitate Substances 0.000 description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910052750 molybdenum Inorganic materials 0.000 description 7
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- 238000005119 centrifugation Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
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- 239000011259 mixed solution Substances 0.000 description 5
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910017116 Fe—Mo Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
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- 150000003624 transition metals Chemical class 0.000 description 3
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- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 description 2
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- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- YECIFGHRMFEPJK-UHFFFAOYSA-N lidocaine hydrochloride monohydrate Chemical compound O.[Cl-].CC[NH+](CC)CC(=O)NC1=C(C)C=CC=C1C YECIFGHRMFEPJK-UHFFFAOYSA-N 0.000 description 1
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- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
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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
-
- 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
- C25B1/28—Per-compounds
- C25B1/30—Peroxides
-
- 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 belongs to the technical field of electrocatalysis, and particularly relates to a surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material, and a preparation method and application thereof. Dissolving iron salt and molybdenum salt in a solvent, and synthesizing an oxide precursor by using a hydrothermal method; annealing the oxide precursor to obtain a nitride precursor; and (4) carrying out annealing treatment on the nitride precursor to obtain the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material. The surface nitrogen-oxygen co-doped iron-molybdenum bimetal material provided by the invention is used for electrocatalysis of O 2 Synthesis of H 2 O 2 Mainly to solve the existing H 2 O 2 Large energy consumption and large environmental pollution in the industrial production process. The preparation method has the advantages of simple process, convenient operation and low cost investment, and the prepared surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material can directly catalyze O 2 Generation of H 2 O 2 . The material prepared by the invention is used in electrocatalysis and sectionHas important application value in the fields of emission reduction and the like.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to preparation of a surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material and application of the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material in electrocatalysis of O 2 Synthesis of H 2 O 2 Application of the aspect.
Background
Hydrogen peroxide (H) 2 O 2 ) As an important inorganic compound, the compound is widely applied to disinfection, cleaning, bleaching, oxidation and other links in production and life. At present, H 2 O 2 The industrial synthesis method still depends heavily on expensive and energy-consuming anthraquinone redox reaction, and more economical and efficient H is developed 2 O 2 The synthesis process is one of the hot spots and difficulties at the technological front in the world. As an emerging technology, O is electrically reduced 2 Preparation H 2 O 2 The method is a normal-temperature preparation scheme with great application prospect, but the technology is still greatly limited by short plates with weak activity, low selectivity and the like of the electrocatalyst at present. Although the noble metal catalysts such as Au, Pt, Pd-Au, Pt-Hg, etc. reported in the literature can satisfy the requirements of high activity and high selectivity, most of them are faced with the problems of high cost, scarcity, even high toxicity, etc.
The transition metal molybdenum has rich natural resources, low price, good conductivity and special valence-layer electronic structure 4d 5 5s 1 The catalyst is easy to show Pt-like behavior, forms stable metal bonds and has excellent electrocatalytic activity. China is the most abundant world molybdenum resource, accounts for 40% of the global reserves, and does not belong to the material of 'neck card'. However, because the single molybdenum metal active site is single, the condition of electron aggregation is easily formed on the surface, the electronic structure is difficult to regulate and control, and the optimization of catalytic activity is difficult to realize. Researches show that the introduction of the bimetallic material enables electronic structures between two metals to be modified mutually, so that more effective active sites are formed, and the catalytic reaction is promoted to be carried out. Therefore, we have introduced the concept of molybdenum-based bimetallic compounds, incorporating the transition metal iron on the basis of the metal molybdenum.
Both oxynitride-doped iron and oxynitride-doped molybdenum alone have been reported in the literature. Document 1 (Melissa E. Kreider, Jens K. N Bronsto rstov Nitride or Oxynteride Eluidizing the Composition-Activity Relationships in Molybdenum Nitride Elfin catalysis for the Oxygen Reduction Reaction [ J]. Chem. Mater2020, 32, 2946-2960.) reports the use of monometallic molybdenum oxynitride-doped materials in electrocatalytic oxygen reduction reactions, indicating that molybdenum nitride doped with moderate oxygen content has excellent electrocatalytic O 2 Synthesis of H 2 O 2 And (4) performance.
Chinese patent application CN114180549A discloses a preparation method of a carbon material containing 3d metal single atoms and nitrogen and oxygen co-doped. The used working electrode material is used as an electrocatalyst for producing hydrogen peroxide by oxygen reduction, the electrocatalytic initial potential reaches 0.75V relative to a reversible hydrogen electrode, the selectivity exceeds 95 percent, and the high-activity and high-selectivity are shown in the reaction of producing hydrogen peroxide by oxygen reduction. However, the patent of the invention does not show quantitative data of the successful synthesis of hydrogen peroxide. In addition, the nitrogen-oxygen co-doped metal materials in the existing design are all based on carbon-based carriers. No separate nitrogen-oxygen doped metallic material has been seen.
Disclosure of Invention
Aiming at the existing H 2 O 2 The problems of large energy loss, large environmental pollution and the like in the industrial production process, and electrocatalysis of O 2 Synthesis of H 2 O 2 The technology is still largely limited by the short plates of the electrocatalyst, such as weak activity, low selectivity, etc. The invention provides a surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material.
The invention also provides a preparation method of the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material.
The invention further provides the application of the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material in electrocatalysis of O 2 Synthesis of H 2 O 2 Application of the aspect.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a surface nitrogen-oxygen co-doped iron-molybdenum bimetal material comprises the following steps:
(1) preparing an oxide precursor: dissolving iron salt and molybdenum salt in a solvent, and synthesizing an oxide precursor by using a hydrothermal method;
(2) preparation of nitride precursor: annealing the oxide precursor to obtain a nitride precursor;
(3) surface nitrogen and oxygen co-doped iron-molybdenum bimetallic material: and (4) carrying out annealing treatment on the nitride precursor to obtain the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material.
Further, the solvent in the step (1) is distilled water.
Further, in the step (1), the ferric salt is at least one of ferrous sulfate, ferrous chloride and ferrous ammonium sulfate, and the molybdenum salt is at least one of sodium molybdate and ammonium molybdate.
Further, the mass ratio of the iron salt to the molybdenum salt in the step (1) is 1 (0.1-100).
Further, the heating temperature of the hydrothermal method in the step (1) is 50-300 ℃, preferably 120 ℃, and the heating time is 0.5-48h, preferably 24-36 h.
Further, the annealing atmosphere in the step (2) is ammonia gas.
Further, the annealing temperature in the step (2) is 500-800 ℃, preferably 800 ℃, and the annealing time is 0.5-10h, preferably 5-7 h.
Further, the fire atmosphere in the step (3) is air.
Further, the annealing temperature in the step (3) is 100-800 ℃, preferably 300 ℃, and the annealing time is 1-60min, preferably 5-15 min.
The preparation method provided by the invention is adopted to prepare the surface nitrogen-oxygen co-doped iron-molybdenum bimetal material by doping nitrogen and oxygen with double transition metals.
The surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material disclosed by the invention is used for electrocatalysis of O 2 Synthesis of H 2 O 2 The material can effectively convert O 2 Conversion to H 2 O 2 . When in application, the method comprises the following specific steps: surface nitrogen and oxygen prepared in the step (3)And (3) grinding the codoped iron-molybdenum bimetallic material, adding a proper amount of absolute ethyl alcohol and Nafion membrane solution, and performing ultrasonic homogenization to obtain slurry. Uniformly coating the slurry on a current collector to serve as a working electrode, performing an electro-catalysis experiment, and measuring H 2 O 2 The yield of (2).
The reaction mechanism of the present invention: generation of H 2 O 2 The electrocatalytic oxygen reduction pathway of (a) generally involves two events in acidic and basic media:
in the acidic medium, the acid-base catalyst is added,
(1) O 2 +2H + +2e - =H 2 O 2 E 0 =0.70V (vs. RHE)
(2) O 2 +*+2(H + +e - )=*OOH+(H + +e - )=H 2 O 2 +*
in the alkaline medium, the alkaline medium is added with a solvent,
(3) O 2 +H 2 O+2e - =HO 2 - +OH - E0=0.76V (vs. RHE)
(4) O 2 +*+H 2 O+2e - =*OOH+OH - +e - =HO 2 - +OH - +*
wherein x represents an unoccupied active site and OOH represents a single adsorption intermediate of the reaction. For selective 2 e-transfer, a catalyst with moderate binding energy to OOH is required. It cannot be too strong nor too weak. Strong binding energy results in a large overpotential, while weak binding energy reduces activity. Whereas electrocatalytic reactions generally take place at the surface of the catalyst. Therefore, the surface of the iron-molybdenum bimetal is simultaneously modified by nitrogen and oxygen, the Fermi level is reduced, and the moderate binding energy of the surface of the catalyst to OOH can be adjusted.
The invention has the following beneficial effects:
1. compared with the existing iron-molybdenum bimetallic material, the surface nitrogen-oxygen co-doping material is designed, so that the 2e can be greatly improved - ORR capacity, enhancement of 2e under neutral conditions - Stability of ORR. The strategy is to increase the electrocatalytic O 2 Synthesis of H 2 O 2 Provides a new idea.
2. The invention simplifies the preparation steps without increasing the process flow, has low requirements on raw material materials, wide raw material sources and low price, and greatly reduces the requirements on working procedures and devices because the Chinese molybdenum resource accounts for 40 percent of the world. To a certain extent by O 2 Electrocatalytic synthesis of H 2 O 2 The development of (2) widens the road.
3. Solvents and raw materials used in the experimental process of each step are strictly screened, so that the method has fewer by-products and higher yield.
4. The method is simple to operate, low in cost and suitable for large-scale production. The working electrode prepared from the material prepared by the invention has good working efficiency, and at the laboratory stage, the working electrode is prepared by electro-catalyzing O under neutral conditions 2 Synthesis of H 2 O 2 One of the best performing catalysts, in H 2 O 2 The synthesis field has important application value.
Drawings
FIG. 1 is a synthesis flow chart of a surface nitrogen-oxygen co-doped iron-molybdenum bimetal material;
FIG. 2 is an X-ray diffraction diagram of the nitrogen-oxygen co-doped Fe-Mo bimetal material and the nitride precursor on the surface in example 1;
FIG. 3 is an XPS plot of the surface nitrogen-oxygen co-doped Fe-Mo bimetallic material and precursor of example 1;
FIG. 4 shows the surface nitrogen and oxygen co-doped Fe-Mo bimetal material in example 1 in 2e - Current density plot at 0v (vs rhe) in ORR process;
fig. 5 is a diagram of a solid hydrogen peroxide substance produced by using the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material in example 1 after catalyzing for 18 hours.
Detailed Description
The following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation processes are given, but the scope of the invention is not limited by the following examples.
Example 1
A preparation method of a surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material comprises the following steps:
(1) preparing an oxide precursor: firstly, 1.2mmol of ferrous chloride (FeCl) 2 ·4H 2 O) was added to 15mL of distilled water, and then 1.2mmol of sodium molybdate (Na) was added to the above solution with stirring 2 MoO 4 ). After the mixed solution was stirred for 5 minutes, 50mL of polytetrafluoroethylene was further added to the reactor, and the reaction was carried out at 120 ℃ for 24 hours. After centrifugation, the centrifuged precipitate was repeatedly washed with ethanol and distilled water to completely remove the unreacted reagent. Then, further drying the obtained precipitate in vacuum, and drying the precipitate in a 60 ℃ oven for about 12 hours to obtain oxide precursor powder;
(2) preparation of nitride precursor: in a tube furnace with 10 sccm continuous ammonia flow, putting the oxide precursor powder at 800 ℃ for annealing treatment for 5h to obtain nitride precursor powder;
(3) surface nitrogen and oxygen co-doped iron-molybdenum bimetallic material: and (3) heating the nitride precursor in a muffle furnace at 300 ℃ for 5min to obtain the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material.
The synthetic flow chart of the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material prepared in example 1 is shown in fig. 1.
Fig. 2 is an X-ray diffraction diagram of a surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material and a nitride precursor, and it can be seen from the analysis of the crystal phase in fig. 2 that the main component of the sample is the desired material and no other substances exist. Compared with the nitride precursor, the peak of the iron-molybdenum bimetallic material co-doped with nitrogen and oxygen on the surface has no obvious change in the position, but has weakened strength. The successful preparation of the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material is demonstrated.
FIG. 3 is an XPS diagram of a surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material and a precursor; as can be seen from the XPS graph, the signal measured by XPS detects clear evidence of the coexistence of N and O signals in the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material. Specifically, the binding energy of 396.2 and 394.1 eV in the surface nitrogen-oxygen co-doped iron-molybdenum bimetal material is attributed to N1s, and the peak value of O1s is located at 528.9 and 529.9 eV. It is worth noting that by comparing pure oxides and nitrides, XPS peak shift occurs in surface nitrogen-oxygen co-doped iron-molybdenum bimetallic materials, possibly due to nitrogen-oxygen co-doping effect in bimetallic catalysts. Further illustrates that the iron-molybdenum bimetallic material with surface nitrogen-oxygen co-doping is successfully prepared.
Example 2
A preparation method of a surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material comprises the following steps:
(1) preparing an oxide precursor: firstly, 1.2mmol of ferrous chloride (FeCl) 2 ·4H 2 O) was added to 15mL of distilled water, and then 1.2mmol of sodium molybdate (Na) was added to the above solution with stirring 2 MoO 4 ) And (3) solution. After the mixed solution was stirred for 5 minutes, 50mL of polytetrafluoroethylene was further added to the reactor, and the reaction was carried out at 120 ℃ for 36 hours. After centrifugation, the centrifuged precipitate was repeatedly washed with ethanol and distilled water to completely remove the unreacted reagent. Then, further drying the obtained precipitate in vacuum, and drying the precipitate in a 60 ℃ oven for about 12 hours to obtain oxide precursor powder;
(2) preparation of nitride precursor: in a tube furnace with 10 sccm continuous ammonia flow, putting the oxide precursor powder at 800 ℃ for annealing treatment for 5h to obtain nitride precursor powder;
(3) surface nitrogen and oxygen co-doped iron-molybdenum bimetallic material: and (3) heating the nitride precursor in a muffle furnace at 300 ℃ for 5min to obtain the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material.
Example 3
A preparation method of a surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material comprises the following steps:
(1) preparation of oxide precursor: firstly, 1.2mmol of ferrous chloride (FeCl) 2 ·4H 2 O) was added to 15mL of distilled water, and then 15mL of 0.08mol of sodium molybdate (Na) was added to the above solution under stirring 2 MoO 4 ) And (3) solution. After the mixed solution was stirred for 5 minutes, 50mL of polytetrafluoroethylene was further added to the reactor, and the reaction was stirred at 120 ℃ for 24 hours. After centrifugation, the centrifuged precipitate was repeatedly washed with ethanol and distilled water to completely remove the unreacted reagent. Then the obtained precipitate is further processedVacuum drying, and drying in a 60 ℃ oven for about 12h to obtain oxide precursor powder;
(2) preparation of nitride precursor: in a tube furnace with 10 sccm continuous ammonia flow, putting the oxide precursor powder at 800 ℃ for annealing treatment for 7h to obtain nitride precursor powder;
(3) surface nitrogen and oxygen co-doped iron-molybdenum bimetallic material: and (3) heating the nitride precursor in a muffle furnace at 300 ℃ for 5min to obtain the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material.
Example 4
A preparation method of a surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material comprises the following steps:
(1) preparing an oxide precursor: firstly, 1.2mmol of ferrous chloride (FeCl) 2 ·4H 2 O) was added to 15mL of distilled water, and then 15mL of 0.08mol of sodium molybdate (Na) was added to the above solution under stirring 2 MoO 4 ) And (3) solution. After the mixed solution was stirred for 5 minutes, 50mL of polytetrafluoroethylene was further added to the reactor, and the reaction was stirred at 120 ℃ for 24 hours. After centrifugation, the centrifuged precipitate was repeatedly washed with ethanol and distilled water to completely remove the unreacted reagent. Then, further drying the obtained precipitate in vacuum, and drying the precipitate in a 60 ℃ oven for about 12 hours to obtain oxide precursor powder;
(2) preparation of nitride precursor: in a tube furnace with 10 sccm continuous ammonia flow, putting the oxide precursor powder at 800 ℃ for annealing treatment for 5h to obtain nitride precursor powder;
(3) surface nitrogen and oxygen co-doped iron-molybdenum bimetallic material: and (3) heating the nitride precursor in a muffle furnace at 300 ℃ for 10min to obtain the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material.
Example 5
A preparation method of a surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material comprises the following steps:
(1) preparing an oxide precursor: firstly, 1.2mmol of ferrous chloride (FeCl) 2 ·4H 2 O) was added to 15mL of distilled water, and then 15mL of 0.08mo was added to the above solution with stirringSodium molybdate (Na) 2 MoO 4 ) And (3) solution. After the mixed solution was stirred for 5 minutes, 50mL of polytetrafluoroethylene was further added to the reactor, and the reaction was stirred at 120 ℃ for 24 hours. After centrifugation, the centrifuged precipitate was repeatedly washed with ethanol and distilled water to completely remove the unreacted reagent. Then, further drying the obtained precipitate in vacuum, and drying the precipitate in a 60 ℃ oven for about 12 hours to obtain oxide precursor powder;
(2) preparation of nitride precursor: in a tube furnace with 10 sccm continuous ammonia flow, the oxide precursor powder is placed at 800 ℃ for annealing treatment for 5h to obtain nitride precursor powder;
(3) surface nitrogen and oxygen co-doped iron-molybdenum bimetallic material: and (3) heating the nitride precursor in a muffle furnace at 200 ℃ for 15min to obtain the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material.
Performance application test:
the working electrode prepared by the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material of the example 1 is used for electrocatalysis test.
After the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material prepared in example 1 is ground, a proper amount of absolute ethyl alcohol and a Nafion membrane solution are added, and slurry is obtained after ultrasonic homogenization. Uniformly coating the slurry on a current collector to serve as a working electrode, performing an electro-catalysis experiment, and measuring H 2 O 2 The yield of (2).
FIG. 4 shows the surface nitrogen and oxygen co-doped Fe-Mo bimetal material in example 1 in 2e - Current density plot at 0v (vs rhe) in ORR process; FIG. 4 summarizes 10 mA/cm at 0V (Vs RHE) 2 The stability of the catalyst during the 18 hour experiment was demonstrated by the stable current density of (g).
Fig. 5 is a diagram of a solid hydrogen peroxide substance produced by using the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material in example 1 after catalyzing for 18 hours.
The performance of the working electrode prepared by the nitrogen and oxygen co-doped iron-molybdenum bimetal material with the middle surface in the examples 2-5 is equivalent to that in the example 1.
Although the present invention has been illustrated and described with reference to specific examples, it should be understood that the present invention is not limited to the details of the foregoing embodiments, and that various changes, modifications, substitutions, combinations and omissions may be made without departing from the spirit and scope of the invention.
Claims (8)
1. The preparation method of the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material is characterized by comprising the following steps of:
(1) preparing an oxide precursor: dissolving iron salt and molybdenum salt in a solvent, and synthesizing an oxide precursor by using a hydrothermal method;
(2) preparation of nitride precursor: annealing the oxide precursor prepared in the step (1) to obtain a nitride precursor;
(3) preparing a surface nitrogen-oxygen co-doped iron-molybdenum bimetal material: and (3) carrying out annealing treatment on the nitride precursor prepared in the step (2) to obtain the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material.
2. The preparation method of the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material according to claim 1, characterized in that: the solvent in the step (1) is distilled water; the iron salt is at least one of ferrous sulfate, ferrous chloride and ferrous ammonium sulfate, and the molybdenum salt is at least one of sodium molybdate and ammonium molybdate.
3. The preparation method of the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material according to claim 1, characterized in that: the mass ratio of the ferric salt to the molybdenum salt in the step (1) is 1 (0.1-100).
4. The preparation method of the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material according to claim 1, characterized in that: the heating temperature of the hydrothermal method in the step (1) is 50-300 ℃, and the heating time is 0.5-48 h.
5. The preparation method of the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material according to claim 1, characterized in that: the atmosphere of the annealing treatment in the step (2) is ammonia gas, the annealing temperature is 500-800 ℃, and the annealing time is 0.5-10 h.
6. The preparation method of the surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material according to claim 1, characterized in that: in the step (3), the annealing atmosphere is air, the annealing temperature is 100-800 ℃, and the annealing time is 1-60 min.
7. The surface nitrogen-oxygen co-doped iron-molybdenum bimetallic material prepared by the preparation method of any one of claims 1-6.
8. The surface nitrogen and oxygen co-doped iron-molybdenum bimetal material of claim 7 in electrocatalysis of O 2 Synthesis of H 2 O 2 Application of the aspect.
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