CN111729680A - High-efficiency bifunctional oxygen electrocatalyst with heterostructure and preparation and application thereof - Google Patents
High-efficiency bifunctional oxygen electrocatalyst with heterostructure and preparation and application thereof Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000001301 oxygen Substances 0.000 title claims abstract description 37
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 37
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 26
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 9
- 239000002135 nanosheet Substances 0.000 claims abstract description 8
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 24
- 238000003763 carbonization Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- -1 iron ions Chemical class 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 229910001313 Cobalt-iron alloy Inorganic materials 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910000531 Co alloy Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 2
- JUDGILXVLDXGHJ-UHFFFAOYSA-N iron;methanol Chemical compound [Fe].OC JUDGILXVLDXGHJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 49
- 239000003792 electrolyte Substances 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003446 ligand Substances 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 229910003321 CoFe Inorganic materials 0.000 description 29
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 5
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- 238000001075 voltammogram Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
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- 239000001257 hydrogen Substances 0.000 description 3
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- 238000005342 ion exchange Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000002057 nanoflower Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910000474 mercury oxide Inorganic materials 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 238000004832 voltammetry Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910020598 Co Fe Inorganic materials 0.000 description 1
- 229910002519 Co-Fe Inorganic materials 0.000 description 1
- 229910002555 FeNi Inorganic materials 0.000 description 1
- 239000013177 MIL-101 Substances 0.000 description 1
- 239000012917 MOF crystal Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910003266 NiCo Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004690 nonahydrates Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
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- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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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
- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a high-efficiency bifunctional oxygen electrocatalyst with a heterostructure, and preparation and application thereof, wherein cobalt nitrate and p-phenylenediamine are dissolved in methanol, uniformly stirred and mixed, and are placed in a reaction kettle for reaction for 8 hours to obtain a flower-shaped amorphous cobalt-based metal organic compound precursor; secondly, the introduction of iron element is realized by utilizing the double-solvent effect and the inclusion of ligand p-phenylenediamine to different metals; and finally, carbonizing the obtained product to obtain the target product. The contact area between the electrolyte and the catalyst is increased by the flower-shaped nanosheet structure, and the conductivity and stability of the catalyst are enhanced by the coating of the graphitized carbon layer. The method is low in cost and easy to operate, and the product has good oxygen reduction (ORR) and Oxygen Evolution (OER) electrocatalytic activity in alkaline electrolyte and has potential application value in the fields of energy conversion and storage.
Description
Technical Field
The invention belongs to the technical field of catalysts, and relates to a high-efficiency bifunctional oxygen electrocatalyst with a heterostructure, and preparation and application thereof.
Background
In recent years, the energy crisis and environmental pollution have driven and accelerated the inevitable shift from fossil fuels to clean renewable energy, and the development of renewable energy storage and conversion devices, in which fuel cells and metal-air batteries play an important role in such energy conversion, is at a premium. Research has found that Oxygen Reduction Reaction (ORR) during discharge of oxygen electrode and Oxygen Evolution (OER) during charge involve multiple electron/proton transfer processes, the kinetics are very slow, which largely hampers the commercialization and large-scale application of these new devices, and large amounts of catalyst are usually required to accelerate the reaction. Currently, the noble metals platinum and ruthenium/iridium-based oxides are considered to be the best ORR and OER catalysts, respectively, however noble metal catalysts are scarce in storage, costly, poor in durability and single in function and cannot catalyze both reactions simultaneously. Therefore, there is a need to design and develop a non-noble metal bifunctional oxygen electrocatalyst that is highly efficient and inexpensive.
The heteroatom-doped carbon-loaded bimetallic alloy (CoFe, NiCo and FeNi) composite material can have certain selectivity for different catalytic reactions due to unique double active sites and rich valence conversion, and in addition, the electronic structure of the composite material can be effectively modified through interaction between metals, so that the surface energy of the catalyst is adjusted, and the binding energy of hydroxyl radicals and the surface of a catalytic material is optimized. The synthesis method of the existing bimetallic alloy catalyst mainly comprises the following steps: (i) metal salts and nitrogen-rich small molecule precursors are pyrolyzed at high temperature on a carbon substrate. Dicyandiamide and melamine are commonly used carbon and nitrogen precursors for preparing the nitrogen-doped graphitized carbon-coated bimetallic nanoparticle oxygen electrocatalyst, the one-step solid pyrolysis method is simple and easy to implement, but the uncontrollable size and structure of the nanoparticles greatly limit the catalytic activity of the material. (ii) Pyrolyzing the metal organic framework. Traditional MOF derived materials have predominantly simple MOF crystals as single precursors, however most simple MOFs are mononuclear metals, and the integration of two or more metals into a single MOF has become a problem. At present, the bimetallic alloy composite material is generally prepared by a double MOF assisted pyrolysis method. For example, Zhang et al, B.Y. guan and X.W.D.Lou, Small,2019,15,1805324, have added complexity to the experiment by selecting Fe-based MIL-101 and Co-based ZIF-67 as precursors for the synthesis of Co-Fe alloy/NC catalysts. In addition, in order to preserve the porosity and integrity of the MOF structure, pyrolysis is usually selected at a lower temperature, but the catalytic material synthesized in this way often has the problems of low graphitization degree, reduced interaction between the active metal nanoparticles and the conductive carbon layer, and the like, and the activity and stability of the material are greatly reduced.
Therefore, how to further improve the stability and catalytic activity of the catalyst is particularly necessary. The present invention has been made in view of the above problems.
Disclosure of Invention
The invention aims to provide a high-efficiency bifunctional oxygen electrocatalyst with a heterostructure, and preparation and application thereof. P-phenylenediamine with good inclusion is adopted as a ligand, and bimetal is introduced into an organic compound by virtue of the double-solvent effect of n-hexane and methanol. After high-temperature carbonization, the target product still maintains the original sheet structure of the precursor and generates a thin graphitized carbon layer, thereby increasing the stability of the catalyst. More interestingly, during the ion exchange process, some porous structures are generated on the nano-sheets, so that the specific surface area of the material is increased, more active sites are exposed, and the catalytic activity of the material is facilitated.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a high-efficiency bifunctional oxygen electrocatalyst with a heterostructure, which is formed by loading cobalt/cobalt-iron alloy heterogeneous nanoparticles on a nitrogen-doped porous carbon nanosheet.
The second technical scheme of the invention provides a preparation method of a high-efficiency bifunctional oxygen electrocatalyst with a heterostructure, which is characterized by comprising the following steps:
(1) taking soluble cobalt salt and p-phenylenediamine as raw materials, dispersing the raw materials in a solvent, uniformly mixing, heating for reaction, cooling, separating and drying to obtain a cobalt-based metal organic compound precursor (namely a Co-PPD precursor);
(2) dispersing the cobalt-based metal organic compound precursor into n-hexane, adding a soluble iron salt methanol solution, stirring to introduce iron ions into the cobalt-based metal organic compound precursor, centrifugally drying the obtained product, and carbonizing to obtain the target product, namely the high-efficiency bifunctional oxygen electrocatalyst Co/CoFe @ NC.
Further, in the step (1), the soluble cobalt salt is cobalt nitrate, and the solvent is methanol.
Further, in the step (1), the mass ratio of the soluble cobalt salt to the p-phenylenediamine is (0.3-1.2): (0.8-1.2), the volume of the methanol is 5-20mL for every 0.8-1.2g of p-phenylenediamine.
Further, in the step (1), the heating reaction temperature is 90-140 ℃, and the reaction time is 6-10 h.
Further, in the step (2), the soluble ferric salt is ferric nitrate.
Further, in the step (2), the volume of the added n-hexane is 10-20mL, the concentration of ferric nitrate is 10-25mg/L, and the dropping volume is 140-.
Further, in the step (2), the stirring time is 0.5-1.5 h.
Further, in the step (2), the carbonization temperature is 750-. Furthermore, the heating rate is 1-5 ℃/min.
Further, a methanol solution of a soluble iron salt was added dropwise to n-hexane.
According to the invention, cobalt nitrate and p-phenylenediamine are respectively used as a metal source and a ligand, and the strong binding capacity of an amino functional group at a special position in the p-phenylenediamine to metal ions is utilized in the hydrothermal synthesis process to form Co-PPD. If the amount of p-phenylenediamine is too large in this step, it itself polymerizes into spheres, and if it is too small, the metal ions cannot coordinate to form a complex. And then, iron ions are hydrolyzed to generate hydrogen ions, a part of cobalt is dissolved out to carry out ion exchange, and the iron ions are successfully introduced into the precursor complex. In the process, methanol is required to be used when preparing the ferric nitrate solution, and other solvents are dropwise added into n-hexane to cause the agglomeration of Co-PPD; the iron ions are uniformly dispersed in the solution by the ultrasonic dispersion during the dripping process. Finally, high-temperature carbonization is carried out to convert the precursor into a nitrogen-doped porous carbon nanosheet modified by cobalt/cobalt-iron alloy heterogeneous nanoparticles, and the carbonization temperature is too high, so that the nanoparticles are agglomerated and the active sites are reduced; when the temperature is too low, the graphitization degree of the catalyst is not strong, so that the conductivity of the catalyst is poor.
The third technical scheme of the invention provides application of the high-efficiency bifunctional oxygen electrocatalyst with a heterostructure, which is characterized in that the oxygen electrocatalyst is used in ORR and OER under alkaline conditions.
The contact area between the electrolyte and the catalyst is increased by the flower-shaped nanosheet structure, and the conductivity and stability of the catalyst are enhanced by the coating of the graphitized carbon layer. The method is low in cost and easy to operate, and the product has good oxygen reduction (ORR) and Oxygen Evolution (OER) electrocatalytic activity in alkaline electrolyte and has potential application value in the fields of energy conversion and storage.
Compared with the prior art, the invention has the following advantages:
(1) the structure is stable. Conventional simple MOFs would choose high temperature pyrolysis in order to enhance the conductivity of the catalyst, but would typically result in structural collapse. The Co/CoFe @ NC catalyst prepared by the invention maintains a precursor Co-PPD nanoflower structure, increases the contact area of a catalytic material and an electrolyte, and can generate cation vacancies in the process of ion exchange, and a large number of mesopores are left on the nanosheets after high-temperature pyrolysis, so that the specific surface area of the material is increased, and the permeation of the electrolyte and the transmission of ions in the reaction process are facilitated, and more catalytic active sites are released.
(2) And (5) interface construction. The Co/CoFe heterostructure constructed by the invention effectively promotes charge transfer, and the interface of the heterostructure can be used as a main catalytic active site to accelerate the dynamics of ORR and OER.
Drawings
FIG. 1-1 is an infrared spectrum of the precursor Co-PPD prepared in example 1 of the present invention;
FIGS. 1-2 are X-ray diffraction (XRD) spectra of the precursor Co-PPD prepared in example 1 of the present invention;
FIGS. 1-3 are scanning electron micrographs (SEM, c-d) of the Co-PPD precursor prepared in example 1 of the present invention;
FIGS. 1-4 are elemental distribution diagrams (e-h) of the precursor Co-PPD prepared in example 1 of the present invention;
FIG. 2-1 is an X-ray diffraction (XRD) spectrum (a) of the catalyst Co/CoFe @ NC prepared in example 2 of the present invention;
FIG. 2-2 is a Raman spectrum of the catalyst Co/CoFe @ NC prepared in example 2 of the present invention;
FIGS. 2-3 are scanning electron micrographs (SEM, c-d) of the catalyst Co/CoFe @ NC prepared in example 2 of the present invention;
FIGS. 2-4 are transmission electron micrographs (TEM, e-f) of the catalyst Co/CoFe @ NC prepared in example 2 of the present invention;
FIGS. 2-5 are elemental distribution plots (g-k) for the catalyst Co/CoFe @ NC prepared in example 2 of the present invention;
FIG. 3 is an X-ray photoelectron Spectroscopy (XPS) of the Co/CoFe @ NC catalyst prepared in example 2 of the present invention;
FIG. 4-1 shows the catalyst Co/CoFe @ NC prepared in example 2 of the present invention and a commercial catalyst RuO2Linear sweep voltammogram (a) and corresponding tafel slope plot (b) at 1M potassium hydroxide electrolyte;
FIG. 4-2 is a plot of cyclic voltammetry for the Co/CoFe @ NC catalyst prepared in example 2 of the invention at different sweep rates;
FIGS. 4-3 are graphs of current density difference versus different sweep rates for a Co/CoFe @ NC catalyst at a relative reduced hydrogen potential of 0.13V;
FIGS. 4-4 are impedance profiles of different electrodes;
FIGS. 4-5 are stability plots for Co/CoFe @ NC electrodes;
FIG. 5-1 is a plot of linear sweep voltammogram (a) and corresponding Tafel slope values (b) of the catalyst Co/CoFe @ NC prepared in example 2 of the present invention with a commercial catalyst Pt/C (20%) in 0.1M KOH electrolyte;
FIG. 5-2 is a plot of linear sweep voltammograms at different rotational speeds and K-L at different potentials for the catalyst Co/CoFe @ NC prepared in example 2 of the present invention;
FIGS. 5-3 are graphs showing the stability of the Co/CoFe @ NC catalyst prepared in example 2 of the invention;
FIGS. 5-4 are dual function LSV curves for different electrodes;
FIGS. 5-5 are graphs showing bifunctional OER and ORR activities of the catalyst Co/CoFe @ NC prepared in example 2 of the present invention with other catalysts previously reported;
FIG. 6 is a flow chart of the manufacturing process of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, potassium hydroxide, n-hexane and methanol were obtained from Merlne Biotech, Inc. of Shanghai, and p-phenylenediamine, nonahydrate, ferric nitrate and cobalt nitrate hexahydrate were obtained from Allantin reagent, Inc. (Shanghai). The remaining raw material products or processing techniques which are not specifically described are conventional commercial products or conventional processing techniques in the art.
Electrochemical data were collected by CHI760E (shanghai chenhua) and a rotating disk test system.
Example 1:
preparation of precursor Co-PPD, as shown in FIG. 6:
(1) weighing p-phenylenediamine and cobalt nitrate, respectively dissolving the p-phenylenediamine and the cobalt nitrate in methanol with the same volume, stirring and dissolving, wherein the mass of the p-phenylenediamine is 1.0g, the mass of the cobalt nitrate is 0.9g, and the volume of the methanol is 20 mL;
(2) and (2) rapidly mixing and stirring the two solutions in the step (1), and then transferring the two solutions into a polytetrafluoroethylene inner container for solvothermal pretreatment, wherein the reaction temperature is 120 ℃, and the reaction time is 8 hours. And after the reaction is finished, cooling to room temperature, centrifuging to remove impurities, collecting, and finally drying in a vacuum drying oven at 80 ℃ for 10h to obtain the Co-PPD precursor.
Example 2:
preparation of Co/CoFe @ NC bifunctional catalyst, as shown in FIG. 6:
(1) weighing the Co-PPD in example 1, ultrasonically dispersing in n-hexane, preparing a ferric nitrate methanol solution, dropwise adding the ferric nitrate methanol solution into the solution, and continuously stirring for 1h after dropwise adding, wherein the mass of the Co-PPD is 50mg, the volume of the n-hexane is 12mL, the ultrasonic time is 1h, the concentration of ferric nitrate is 25mg/L, and the dropwise adding volume is 280 mu L.
(2) And (2) carbonizing the product in the step (1) in an argon protection environment to obtain the Co/CoFe @ NC dual-function oxygen electrocatalyst, wherein the carbonization temperature is 850 ℃, the carbonization time is 3h, and the heating rate is 3 ℃/min.
FIG. 1-1 shows the infrared spectra of ligand PPD and precursor Co-PPD, from which it can be seen that the stretching vibration intensity of-N-H functional group in Co-PPD is weakened, indicating that metal ion is successfully chelated on the amino functional group of ligand. FIGS. 1-2 are XRD representations of Co-PPD with no significant peaks, indicating an amorphous structure. FIGS. 1-3 and 1-4 are SEM and element distribution diagrams of Co-PPD, and the precursor is in the shape of nanoflower with cobalt and nitrogen uniformly dispersed on the surface.
Fig. 2-1 and 2-2 are XRD and raman diagrams of the bifunctional oxygen electrocatalyst prepared upon dropwise addition of different volumes of ferric nitrate solutions, respectively, and it can be seen that catalysts of different compositions can be obtained by effective control of iron ions, wherein a target product of a heterostructure is obtained with a dropwise addition volume of 280 μ L, which has the highest graphitization degree. FIGS. 2-3 and 2-4 show the morphology characterization of Co/CoFe @ NC, which shows that the precursor nanoflower structure is retained, the carbonized nanoparticles are uniformly dispersed on the porous nitrogen-doped carbon nanosheets, and the cobalt simple substance and the cobalt-iron alloy form a heterogeneous interface. The elemental profiles of the products of fig. 2-5 show that the products are composed primarily of the four elements C, N, Fe, and Co, and are formed from cobalt-iron alloys.
FIG. 3 is an XPS characterization of the elements in the product Co/CoFe @ NC, from which it can be seen that nitrogen was successfully doped into the carbon lattice, and the XPS spectrum of the metal shows the valence state 0, confirming the presence of the alloy and the simple substance.
Testing method for preparing Co/CoFe @ NC serving as bifunctional oxygen electrocatalyst
(1) The final product catalyst obtained in example 2 was taken as OER catalyst: the reaction system is a three-electrode system, the graphite rod is a counter electrode, and mercury/mercury oxide is a reference potential. 5mg of the catalyst is weighed and ultrasonically dispersed in 0.49mL of isopropanol and 10 mu L of 5 wt% Nafion to form a uniform suspension, 5 mu L of the suspension is absorbed by a pipette and dropped on a 5mm clean glassy carbon electrode, and the suspension is naturally dried for standby. The electrolyte used in the test was 1M potassium hydroxide. Before testing, the electrode is activated by 50 cycles of cyclic voltammetry scanning, and the scanning speed of a linear voltammetry curve is 5mV s-1. The electrochemical impedance spectrum measured under different overpotentials ranges from 10khz to 0.1hz, and the amplitude is 5 mV. The stability is measured at 10mA cm by constant current time potential method-2The next 12h of continuous testing. The results of the examples are shown in FIGS. 4-1 to 4-4.
RuO, as shown in FIG. 4-1, compared to commercial catalyst2The synthesized Co/CoFe @ NC shows larger current density and lower overpotential, and when the current density is 10mA cm-2When the potential is 0.3V, the potential is opposite to the reversible hydrogen electrode; plot b is the Tafel slope for both, and it can be seen that the Tafel slope value for Co/CoFe @ NC is only 49mV dec-1Far below the catalyst RuO2This indicates that the prepared catalyst has an oxygen evolution kinetic rate superior to that of the noble metal RuO2。
FIG. 4-2 is a cyclic voltammogram of the catalyst at different scan rates, and the difference between the oxidation current and the reduction current at 1.05V is selected to be one half of the capacitance current. The scanning rate is used as an abscissa, the capacitance current under different scanning rates is used as an ordinate, the capacitance current is in direct proportion to the scanning rate, the slope of the line is the double-electric-layer capacitance of the material, and the electrochemical active area is in direct proportion to the double-electric-layer capacitance.
From FIGS. 4-3 and 4-4, it can be seen that the electric double layer capacitance value of Co/CoFe @ NC is 22.8mF cm-2Indicating that it has a large number of oxygen producing active sites. Is worthy ofNote that Co/CoFe @ NC possesses a minimum semicircular diameter (Rct ═ 8.9 Ω) and a steeper slope, confirming its faster charge transfer rate, lower electrode/electrolyte interface resistance, and faster mass diffusion. FIGS. 4-5 show that this catalyst also has good stability.
(2) The final product catalyst obtained in example 2 was taken as OER catalyst: the reaction system is a three-electrode system, the graphite rod is a counter electrode, and mercury/mercury oxide is a reference potential. 5mg of the catalyst was dispersed in 0.49mL of isopropanol and 10. mu.L of 5 wt% Nafion by sonication to form a uniform suspension, and 12. mu.L of the suspension was pipetted onto 5mm clean RDE and allowed to dry. The electrolyte used in the test was 0.1M potassium hydroxide. Before testing, the electrode is activated by 50 cycles of cyclic voltammetry scanning, and the scanning speed of a linear voltammetry curve is 5mV s-1。
FIG. 5-1, panel a, shows the linear sweep voltammogram at 1600rpm on a rotating disk electrode for different catalysts, from which it can be seen that the onset and half-wave potentials are relatively similar, and the Tafel slope of panel b, indicates that Co/CoFe @ NC has faster ORR reaction kinetics.
FIG. 5-2 shows that the K-L curves at different potentials show a good linear relationship, indicating that the first order reaction kinetics of ORR is consistent with the concentration of dissolved oxygen, and the reaction path for catalytic oxygen reduction is dominated by four electrons.
Figures 5-3 show that the catalyst has good stability. The bifunctional linear sweep voltammograms of the different electrodes in fig. 5-4, and the comparisons of fig. 5-5 with previously reported catalysts, demonstrate that Co/CoFe @ NC can be used as an effective bifunctional oxygen electrocatalyst, having potential application values in the energy conversion and storage fields.
Example 3:
compared with the embodiment 1, the method is mostly the same, except that the addition amount of each raw material is changed as follows: the mass of p-phenylenediamine was 0.8g, the mass of cobalt nitrate was 1.2g, and the volume of methanol was 10 mL.
Example 4:
compared with the embodiment 1, the method is mostly the same, except that the addition amount of each raw material is changed as follows: the mass of p-phenylenediamine was 1.2g, the mass of cobalt nitrate was 0.3g, and the volume of methanol was 5 mL.
Example 5:
compared with the embodiment 1, the method is mostly the same, except that in the step (1), the process conditions are respectively changed as follows: the reaction temperature is 90 ℃ and the reaction time is 10 hours; drying in a vacuum drying oven at 60 deg.C for 12 hr.
Example 6:
compared with the embodiment 1, the method is mostly the same, except that in the step (1), the process conditions are respectively changed as follows: the reaction temperature is 140 ℃, and the reaction time is 6 hours; drying in a vacuum drying oven at 120 deg.C for 8 hr.
Example 7:
compared with the embodiment 1, the method is mostly the same, except that the addition amount of each raw material is changed as follows: the mass of Co-PPD is 30mg, the volume of n-hexane is 20mL, the ultrasonic time is 1h, the concentration of ferric nitrate is 20mg/L, and the dropping volume is 140 mu L.
Example 8:
compared with the embodiment 1, the method is mostly the same, except that the addition amount of each raw material is changed as follows: the mass of the Co-PPD is 60mg, the volume of n-hexane is 10mL, the ultrasonic time is 1h, the concentration of ferric nitrate is 10mg/L, and the dropping volume is 560 μ L.
Example 9:
compared with the embodiment 1, the method is mostly the same, except that in the step (2), the process conditions are respectively changed as follows: the carbonization temperature is 750 ℃, the carbonization time is 5h, and the heating rate is 1 ℃/min.
Example 10:
compared with the embodiment 1, the method is mostly the same, except that in the step (2), the process conditions are respectively changed as follows: the carbonization temperature is 950 ℃, the carbonization time is 2h, and the heating rate is 5 ℃/min.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The high-efficiency bifunctional oxygen electrocatalyst with a heterostructure is characterized by being formed by loading cobalt/cobalt-iron alloy heterogeneous nanoparticles on a nitrogen-doped porous carbon nanosheet.
2. A method of preparing a heterostructured high efficiency bifunctional oxygen electrocatalyst according to claim 1, comprising the steps of:
(1) taking soluble cobalt salt and p-phenylenediamine as raw materials, dispersing the raw materials in a solvent, uniformly mixing, heating for reaction, cooling, separating and drying to obtain a cobalt-based metal organic compound precursor;
(2) dispersing the cobalt-based metal organic compound precursor into n-hexane, adding a soluble iron salt methanol solution, stirring to introduce iron ions into the cobalt-based metal organic compound precursor, centrifugally drying the obtained product, and carbonizing to obtain the target product, namely the high-efficiency bifunctional oxygen electrocatalyst.
3. The method for preparing a bifunctional oxygen electrocatalyst with heterostructure according to claim 2, wherein in step (1), the soluble cobalt salt is cobalt nitrate and the solvent is methanol.
4. The method for preparing a high-efficiency bifunctional oxygen electrocatalyst with a heterostructure according to claim 2, wherein in the step (1), the mass ratio of the soluble cobalt salt to the p-phenylenediamine is (0.3-1.2): (0.8-1.2).
5. The method for preparing a bifunctional oxygen electrocatalyst with a heterostructure according to claim 2, wherein in step (1), the heating reaction temperature is 90-140 ℃ and the reaction time is 6-10 h.
6. The method for preparing a high-efficiency bifunctional oxygen electrocatalyst with heterostructure according to claim 2, characterized in that in step (2), the soluble iron salt is ferric nitrate.
7. The method for preparing a high-efficiency bifunctional oxygen electrocatalyst with a heterostructure as claimed in claim 2, wherein in the step (2), the volume of n-hexane added is 10-20mL, the concentration of ferric nitrate is 10-25mg/L, and the dropping volume is 140-560 μ L, calculated by the mass of Co-PPD being 30-60 mg.
8. The method for preparing a bifunctional oxygen electrocatalyst with high efficiency having a heterostructure according to claim 2, wherein in the step (2), the stirring time is 0.5-1.5 h.
9. The method as claimed in claim 2, wherein the carbonization temperature in step (2) is 750-.
10. Use of a high efficiency bifunctional oxygen electrocatalyst with heterostructure according to claim 1, characterized in that it is used in ORR and OER under alkaline conditions.
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