CN110492115B - Fe wrapped by graphene/carbon nanotube frame3C catalyst, preparation and application - Google Patents
Fe wrapped by graphene/carbon nanotube frame3C catalyst, preparation and application Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
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- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 abstract description 7
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- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- SEQUALWBCFCDGP-UHFFFAOYSA-N [C].[N].[Fe] Chemical compound [C].[N].[Fe] SEQUALWBCFCDGP-UHFFFAOYSA-N 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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Abstract
The invention provides a graphene/carbon nanotube framework-wrapped Fe3C catalyst, a preparation method and application thereof, wherein the molecular structure of the catalyst is' Fe3C @ N-F-GCNTs "; the catalyst takes nano-sieve-shaped graphene and bamboo-shaped carbon nanotubes as outer frames, and a metal phase Fe3C is wrapped in the graphene/carbon nanotube frame; the graphene/carbon nanotube framework is N/F double-doped and is rich in edge defect sites. The N, F double-doped graphene/carbon nanotube frame rich in edge defect sites prepared by the method wraps the Fe3C catalyst, PVDF is used as a C source and an F source, iron acetate is used as a Fe source, the catalyst is prepared by adopting 'high-temperature calcination-acid washing-high-temperature calcination', the double doping of N, F elements is realized, and the used raw materials are low in price and easy to obtain.
Description
Technical Field
The invention belongs to the field of energy materials and electrochemistry, and particularly relates to a graphene/carbon nanotube framework coated Fe applied to the fields of fuel cells, metal-air cells and electrolyzed water3C catalystAnd a method for preparing the same.
Background
Global energy and environmental issues have stimulated tremendous research interest in developing sustainable, environmentally friendly energy conversion and storage systems. The development of highly active Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) electrocatalysts is of vital importance for the practical application of fuel cells, metal air cells and water electrolysis technologies. At present, Pt-based catalysts are considered to be the most active ORR catalysts, IrO2 and RuO2 being the most effective OER catalysts. However, their commercialization is severely hampered by the high cost and poor durability associated with the scarcity of precious metal materials. Therefore, a great deal of research effort has been devoted to finding low-cost alternatives with catalytic activity comparable to noble metal-based catalysts. Because of the slow kinetics of ORR and OER, there are significant challenges in developing inexpensive and efficient ORR and OER oxygen electrocatalysts.
Iron-nitrogen-carbon (Fe-N-C) catalysts have become a recent research hotspot due to the advantages of high activity and stability, low price, poison resistance and the like. In particular, recently reported Fe3C nanoparticles contained in Fe-N-C carbon nanostructures have an enhancing effect on ORR and OER electrocatalytic activity. The Fe3C nano-particles coated by the graphite carbon and the surrounding Fe-N doped carbon form a unique synergistic effect, so that the electrocatalytic activity and stability of the catalyst are further improved. However, their ORR and OER performance is still far from satisfactory, probably due to the low conductivity and porosity of the catalyst. Therefore, developing a new carbon-based material with high conductivity and high porosity has a very great challenge.
Carbon nanotubes and graphene have high electrical conductivity and excellent physicochemical properties, and are considered to be very potential electrocatalytic carbon-based supports. Particularly, the 3D interconnected network structure formed by assembling the carbon nanotubes and the graphene can effectively prevent the graphene and the carbon nanotubes from undergoing irreversible agglomeration due to pi-pi stacking and van der Waals interaction. Also, the network may form more accessible cells. Meanwhile, the activity of the catalyst can be further improved by the synergistic effect between the carbon nano tube and the graphene. Therefore, the carbon nanotube and graphene 3D interconnected network hybrid is a very potential electrocatalytic carbon-based support.
At present, the commonly used method for synthesizing 3D graphene and carbon nanotube network structure carbon material mainly includes multi-step Chemical Vapor Deposition (CVD) [ documents Small 2014, 10, 2251-; carbon 2015, 86, 358-.
In summary, the Fe-N-C catalyst coated with Fe3C nanoparticles has good ORR and OER catalytic performance, but the catalytic performance of the catalyst is still far from satisfactory due to the low conductivity and low porosity of the catalyst. The 3D graphene and carbon nanotube net structure carbon carrier with high conductivity and high porosity has very good potential, but the preparation method of the carbon carrier needs to be broken through. Therefore, the efficient 3D graphene and carbon nanotube net structure Fe3C @ Fe-N-C catalyst which is simple in preparation process and low in price has important practical significance and application value.
According to the invention, PVDF with low price is used as a C source and an F source, melamine is used as an N source, ferric acetate is used as an Fe source, and the N, F double-doped graphene filled with edge active sites and the Fe3C nano-particle catalyst wrapped by the carbon nano-tubes are prepared by a high-temperature pyrolysis-acid washing-secondary pyrolysis method and used for oxygen electrocatalytic reaction.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a graphene/carbon nanotube framework-coated Fe3C catalyst and a preparation method thereof, and the catalyst is used as a fuel cell, a metal-air cell and an electrolytic water-oxygen electrocatalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
graphene/carbon nanotube frame wrapped Fe3The molecular structure of the catalyst Fe3C wrapped by the graphene/carbon nanotube framework is' Fe3C @ N-F-GCNTs "; the graphene/carbon nanotube framework is wrapped with Fe3C catalystThe rice-sieve-shaped graphene and the bamboo-shaped carbon nano tube are used as an outer frame, and a metal phase Fe3C is wrapped in the graphene/carbon nanotube frame; the graphene/carbon nanotube framework is N/F double-doped and is rich in edge defect sites.
Further, the thickness of the graphene layer in the graphene/carbon nanotube frame is 2-3 nm.
Further, the thickness of the graphene layer in the graphene/carbon nanotube frame is 2.5 nm.
Metallic phase Fe3C is wrapped by graphene and carbon nano tubes, so that direct contact between the C and electrolyte in the reaction process is effectively avoided, and the stability of the catalyst is improved. The doping of the double hetero atoms provides a large number of doping active sites and simultaneously generates a synergistic effect. Meanwhile, the hole-shaped defects of the graphene provide a large number of edge active sites, and the coated Fe3The C particles can activate the carbon material around the C particles, and the oxygen electrocatalytic activity of the catalyst is further improved.
The second purpose of the invention is to provide Fe wrapped by the graphene/carbon nanotube frame3A method for preparing a catalyst, the method comprising the steps of:
1) mixing melamine, PVDF and Fe (C)2H3O2)2Mixing uniformly to obtain catalyst precursor, wherein Fe (C)2H3O2)2And PVDF in a mass ratio of 0.2 to 2: 1, the mass ratio of melamine to PVDF is 0.5-10: 1;
2) calcining the catalyst precursor obtained in the step 1) under the protection of inert gas, wherein the calcining temperature is 600-1200 ℃, and the heating rate is 2-10 ℃ for min-1The calcination time is 0.5-6h;
3) acid-washing the product obtained in the step 2), washing the acid-washed product to be neutral, and drying; the concentration of the acid is 0.5-3mol L-1Pickling at 30-100 deg.c for 1-48 hr;
4) secondarily calcining the product obtained in the step 3) to obtain a target catalyst; the calcination temperature is 600-1200 ℃, and the heating rate is 2-10 ℃ for min-1The calcination time is 0.5-6 h.
Further, the acid used in step 3) is H2SO4、HClO4、HNO3And HCl, or a mixture of two or more of them.
Further, the drying temperature in the step 3) is 30-90 ℃, and the drying time is 1-48 h.
Further, the washing in the step 3) is water and ethanol washing, low-pressure suction filtration or centrifugal separation; the drying is oven drying, stirring drying or vacuum drying in air atmosphere.
Further, the PVDF described in step 1) may be replaced by PTFE or a mixture of PVDF and PTFE.
Further, the melamine described in step 1) may be replaced by dicyandiamide or a mixture of melamine and dicyandiamide.
The catalyst is prepared by adopting PVDF with low price as a C source and an F source, melamine as an N source and ferric acetate as an Fe source and adopting a method of high-temperature calcination-acid washing-secondary high-temperature calcination. Compared with the commercial Pt/C catalyst, the ORR catalytic activity in alkaline medium is superior to that of the commercial Pt/C catalyst, and the catalyst has higher stability and methanol resistance. And the catalyst has better OER catalytic activity in an alkaline medium, the raw materials are low in price, the preparation process is simple, and the large-scale production is facilitated.
The invention also provides a method for wrapping Fe by the graphene/carbon nanotube frame3Application of C catalyst, wherein graphene/carbon nanotube framework wraps Fe3The C catalyst is used as fuel cell, metal air cell and electrolytic water oxygen electrocatalyst.
Compared with the prior art, the invention has the advantages that:
1) n, F double-doped graphene/carbon nanotube frame-wrapped Fe rich in edge defect positions prepared by adopting method disclosed by the invention3The catalyst C is prepared by using PVDF as a C source and a F source and ferric acetate as a Fe source and adopting 'high-temperature calcination-acid washing-high-temperature calcination', the double doping of N, F elements is realized, and the used raw materials are low in price and easy to obtain;
2) adopt the bookThe N, F double-doped graphene/carbon nanotube framework rich in edge defect sites prepared by the method is wrapped with the graphene/carbon nanotube framework wrapped with the Fe3C catalyst, and Fe (C) is obtained by controlling the preparation conditions2H3O2)2And PVDF in a mass ratio of 0.2 to 2: 1, the mass ratio of melamine to PVDF is 0.5-10: 1, the calcination temperature is 600-1200 ℃, and the heating rate is 2-10 ℃ for min-1The calcination time is 0.5-6h; the catalyst of the invention can be prepared;
3) n, F double-doped graphene/carbon nanotube frame-wrapped Fe rich in edge defect positions prepared by adopting method disclosed by the invention3The preparation process of the catalyst C is simple, economic, safe and good in repeatability, and is beneficial to the amplification production of the catalyst;
4) n, F double-doped graphene/carbon nanotube frame-wrapped Fe rich in edge defect positions prepared by adopting method disclosed by the invention3The catalyst C has ORR catalytic activity superior to that of commercial Pt/C catalyst in alkaline electrolyte, better OER catalytic activity and excellent ORR and OER stability.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a sample prepared according to example 1.
FIG. 2 shows Fe of the present invention3TEM pictures of C @ N-F-GCNTs catalyst.
FIG. 3 is Fe of the present invention3Polarization curve diagram of oxygen electricity double-function catalytic reaction of C @ N-F-GCNTs catalyst in 0.1mol/L KOH solution, scanning speed: 10 mV/s.
Detailed Description
The invention will be explained in more detail below with reference to the accompanying figures 1-3 and examples
Example 1
Graphene/carbon nanotube frame wrapped Fe3And C, adding 2g of melamine, 1g of PVDF and 0.4g of ferric acetate into 25mL of deionized water, stirring in a water bath at 80 ℃ for 2h, drying in a forced air drying oven for 2h, and grinding into powder to obtain a catalyst precursor. Mixing the precursorPlacing into quartz boat, performing heat treatment at 800 deg.C for 2 hr in tube furnace under argon protection, naturally cooling, grinding at 80 deg.C at 1.0M H2SO4Washing in the solution for 12h under reflux, filtering, washing with deionized water to neutrality, performing secondary heat treatment under the same heat treatment condition to obtain the final catalyst, and naming as Fe3C@N-F-GCNTs-800℃。
Example 2
Graphene/carbon nanotube frame wrapped Fe3And C, adding 2g of melamine, 1g of PVDF and 0.4g of ferric acetate into 25ml of deionized water, stirring in a water bath at 80 ℃ for 2h, drying in a forced air drying oven for 2h, and grinding into powder to obtain a catalyst precursor. Putting the precursor into a quartz boat, performing heat treatment at 900 ℃ for 2h in a tube furnace under the protection of argon, naturally cooling, grinding, and performing heat treatment at 80 ℃ of 1.0M H2SO4Washing in the solution for 12h under reflux, filtering, washing with deionized water to neutrality, performing secondary heat treatment under the same heat treatment condition to obtain the final catalyst, and naming as Fe3C@N-F-GCNTs-900℃。
Example 3
Graphene/carbon nanotube frame wrapped Fe3And C, adding 2g of melamine, 1g of PVDF and 0.4g of ferric acetate into 25ml of deionized water, stirring in a water bath at 80 ℃ for 2h, drying in a forced air drying oven for 2h, and grinding into powder to obtain a catalyst precursor. Putting the precursor into a quartz boat, performing heat treatment at 1000 ℃ for 2h in a tube furnace under the protection of argon, naturally cooling, grinding, and performing heat treatment at 80 ℃ of 1.0M H2SO4Washing in the solution for 12h under reflux, filtering, washing with deionized water to neutrality, performing secondary heat treatment under the same heat treatment condition to obtain the final catalyst, and naming as Fe3C@N-F-GCNTs-1000℃。
For Fe prepared in example 23C @ N-F-GCNTs-900 ℃ catalyst is subjected to X-ray diffraction analysis, the result is shown in figure 1, the X axis of the abscissa is the diffraction angle (2 theta), the Y axis of the ordinate is the relative diffraction intensity, a typical strong diffraction peak is shown at 26 degrees, the (002) plane corresponding to graphite carbon is consistent with the structural characteristics of the carbon nano tube.Diffraction peaks at 37.8 °, 43.9 °, 45.0 °, 46.0 °, 49.2 ° and 54.5 ° correspond to Fe3C, consistent with JCPDS-892867 in the International Standard powder XRD diffraction card.
For Fe prepared in example 23The obtained electron picture is shown in figure 2 by analyzing the C @ N-F-GCNTs-900 ℃ catalyst with a transmission electron microscope, and Fe can be seen3C @ N-F-GCNTs-900 ℃ is a reticular graphene sheet layer, a bamboo-shaped carbon nano tube and embedded Fe3C a composite of nanoparticles. Fig. 2c shows that the carbon nanotubes are typically bamboo-like structures. High Resolution TEM (HRTEM) image (FIG. 2d) shows Fe3The C nanoparticles were encapsulated in a 2.5nm thick graphitic carbon layer with a lattice spacing of 0.34nm, due to the (002) plane of the graphite. The graphite carbon layer wraps Fe3The structure of C nanoparticles not only inhibits Fe3The dissolution and agglomeration of the C nano-particles in a harsh alkaline solution can adjust the electron density of the carbon surface, thereby promoting the surface catalytic reaction of the carbon.
For Fe prepared in example 23The analysis result of the C @ N-F-GCNTs-900 ℃ catalyst subjected to linear voltammetry analysis is shown in figure 3, and it can be seen that Fe prepared in the oxygen saturated electrolyte3The C @ N-F-GCNTs-900 ℃ catalyst has catalytic activity superior to that of commercial Pt/C, and simultaneously has better oxygen evolution catalytic activity.
Claims (9)
1. Graphene/carbon nanotube frame wrapped Fe3C catalyst, characterized in that the molecular structure of the catalyst is' Fe3C @ N-F-GCNTs "; the catalyst takes nano-sieve-shaped graphene and bamboo-shaped carbon nanotubes as outer frames, and a metal phase Fe3C is wrapped in the graphene/carbon nanotube frame; the graphene/carbon nanotube frame is N/F double-doped and is rich in edge defect sites;
the thickness of the graphene layer in the graphene/carbon nanotube frame is 2-3 nm.
2. The graphene/carbon nanotube framework encapsulated Fe as claimed in claim 13C catalysisAn agent, wherein the graphene layer in the graphene/carbon nanotube framework has a thickness of 2.5 nm.
3. The graphene/carbon nanotube framework-wrapped Fe of claim 1 or 23The preparation method of the catalyst C is characterized by comprising the following steps:
1) mixing melamine, PVDF and Fe (C)2H3O2)2Mixing uniformly to obtain catalyst precursor, wherein Fe (C)2H3O2)2And PVDF in a mass ratio of 0.2 to 2: 1, the mass ratio of melamine to PVDF is 0.5-10: 1;
2) calcining the catalyst precursor obtained in the step 1) under the protection of inert gas, wherein the calcining temperature is 600-1200 ℃, and the heating rate is 2-10 ℃ for min-1The calcination time is 0.5-6h;
3) acid-washing the product obtained in the step 2), washing the acid-washed product to be neutral, and drying; the concentration of the acid is 0.5-3mol L-1Pickling at 30-100 deg.c for 1-48 hr;
4) secondarily calcining the product obtained in the step 3) to obtain a target catalyst; the calcination temperature is 600-1200 ℃, and the heating rate is 2-10 ℃ for min-1The calcination time is 0.5-6 h.
4. The graphene/carbon nanotube framework encapsulated Fe of claim 33C the preparation method of the catalyst, characterized in that, the PVDF stated in step 1) can be replaced by PTFE or mixture of PVDF and PTFE.
5. The graphene/carbon nanotube framework encapsulated Fe of claim 33The preparation method of the catalyst C is characterized in that the melamine in the step 1) can be replaced by dicyandiamide or a mixture of melamine and dicyandiamide.
6. The graphene/carbon nanotube framework encapsulated Fe of claim 33The preparation method of the catalyst C is characterized in that the catalyst C is used in the step 3)Acid of (A) is H2SO4、HClO4、HNO3And HCl, or a mixture of two or more of them.
7. The graphene/carbon nanotube framework encapsulated Fe of claim 33The preparation method of the catalyst C is characterized in that the drying temperature in the step 3) is 30-90 ℃, and the drying time is 1-48 h.
8. The graphene/carbon nanotube framework encapsulated Fe of claim 33The preparation method of the catalyst C is characterized in that the washing in the step 3) is washing by adopting water and ethanol, and low-pressure suction filtration or centrifugal separation; the drying is oven drying, stirring drying or vacuum drying in air atmosphere.
9. The graphene/carbon nanotube framework of claim 1 or 2 encapsulating Fe3The application of the catalyst C is characterized in that the graphene/carbon nanotube framework wraps Fe3The C catalyst is used as fuel cell, metal air cell and electrolytic water oxygen electrocatalyst.
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| Juanjuan Shi.Synthesis of graphene encapsulated Fe3C in carbon nanotubes from biomass and its catalysis application.《Carbon》.2016,第99卷330-337. * |
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| Synergistic increase of oxygen reduction favourable Fe–N coordination structures in a ternary hybrid of carbon nanospheres/carbon nanotubes/graphene sheets;Shiming Zhang;《Phys. Chem. Chem. Phys》;20130910;第15卷;全文 * |
| Synthesis of graphene encapsulated Fe3C in carbon nanotubes from biomass and its catalysis application;Juanjuan Shi;《Carbon》;20160430;第99卷;第330页右栏第2段、Fig3(d)、supplementary information第2页第6行 * |
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