CN113690452A - Method for preparing catalyst by polymer-metal complex assisted carbonization MOF technology and obtained catalyst - Google Patents
Method for preparing catalyst by polymer-metal complex assisted carbonization MOF technology and obtained catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000003763 carbonization Methods 0.000 title claims abstract description 14
- 238000005516 engineering process Methods 0.000 title claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000243 solution Substances 0.000 claims abstract description 37
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 239000002105 nanoparticle Substances 0.000 claims abstract description 20
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 18
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 10
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
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- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
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- 238000010000 carbonizing Methods 0.000 claims abstract description 3
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- 238000010438 heat treatment Methods 0.000 claims description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000000446 fuel Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
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- 238000002360 preparation method Methods 0.000 description 6
- 239000012528 membrane Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910020676 Co—N Inorganic materials 0.000 description 3
- 102000020897 Formins Human genes 0.000 description 3
- 108091022623 Formins Proteins 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
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- 238000002336 sorption--desorption measurement Methods 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
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- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- LNQCJIZJBYZCME-UHFFFAOYSA-N iron(2+);1,10-phenanthroline Chemical compound [Fe+2].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 LNQCJIZJBYZCME-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical class CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910002556 Fe–N4 Inorganic materials 0.000 description 1
- 229910017108 Fe—Fe Inorganic materials 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
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- 239000011888 foil Substances 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
-
- 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
- Y02E60/50—Fuel cells
Abstract
The invention discloses a method for preparing a catalyst by a polymer-metal complex assisted carbonization MOF technology and the obtained catalyst. The invention firstly discloses a method for preparing a catalyst, which comprises the following steps: dispersing ZIF-8 nanoparticles in a mixed solution of water and ethanol, performing ultrasonic treatment, adding a dopamine hydrochloride monomer and Pluronic F127, and stirring to obtain a dispersion solution; will [ M (Phen)3]2+Dropwise adding ethanol solution into the dispersion liquid, stirring, adjusting the pH to 7.5-10.5, stirring, centrifuging, washing, and drying to obtain a solid substance as a catalyst precursor; carbonizing the catalyst precursor at high temperature to obtain an M-N/C catalyst; wherein M is Fe, Co or Ni. The invention further discloses the catalyst obtained by the method. The method for preparing the catalyst is simple and feasible, and the highly exposed dense FeN is obtained4The catalyst with active sites has excellent oxygen reduction catalytic performance.
Description
Technical Field
The present invention relates to the field of monatomic electrocatalysis. And more particularly to a method for preparing catalysts by polymer-metal complex assisted carbonization MOF technology and the resulting catalysts.
Background
With the progress of human society, the global energy consumption is rapidly increased, the problems of energy crisis, environmental pollution, climate change and the like are more and more prominent, and the development of a clean energy technology which is free of pollution and has high energy conversion efficiency is particularly important. Among them, Proton Exchange Membrane Fuel Cells (PEMFCs) can directly convert chemical energy into electrical energy through electrocatalysis, and have the advantages of low operating temperature, high power density, rapid start, and the like, which have been widely studied by researchers. However, the cathode oxygen reduction (ORR) kinetics of PEMFCs are slow, and commercial Pt/C containing noble metal Pt is used as a catalyst, and the price of the expensive catalyst limits the progress of commercialization of fuel cells. In order to make the fuel cell widely used as early as possible, the development of low-cost non-noble metal catalyst capable of replacing commercial Pt/C becomes a research hotspot in the field of the fuel cell at present.
At present, atomically dispersed Fe-N/C non-noble metal catalysts are considered to be one of the most promising candidates for replacement of commercial platinum carbon catalysts. Having FeN4The active site Fe-N/C monatomic catalyst, although highly active, has a performance that is far from commercial Pt/C. The current common performance optimization method is to increase the metal atom content (namely FeN) in the monatomic catalyst4Active site concentration), however, high temperature pyrolysis is usually adopted in the methods for synthesizing Fe-N/C catalysts, increasing the density of active sites only by increasing the concentration of metallic Fe source often results in a large amount of inactive Fe nanoparticles, reducing the utilization rate of the Fe source, and a cumbersome acid etching step is required to remove the Fe nanoparticles to obtain the monatomic catalyst. On the other hand, the catalyst with reasonable pore structure can fully expose FeN4Active site, can increase FeN4Utilization of active sites.
Therefore, there is a need for a practical and simple method for preparing dense FeN with high exposure4High activity catalyst of active site.
Disclosure of Invention
An object of the present invention is to provide a method for preparing a catalyst by a polymer-metal complex-assisted metal carbide framework (MOF) technique, which is low in raw material cost, simple and easy to implement.
It is another object of the present invention to provide the above method to obtainWith highly exposed dense FeN4The active site shows excellent catalytic performance in the cathode oxygen reduction reaction of the hydrogen-oxygen fuel cell.
In order to achieve the above object, the present invention firstly provides a method for preparing a catalyst by a polymer-metal complex-assisted metal carbide framework compound (MOF) technology, comprising the steps of:
dispersing ZIF-8 nanoparticles in a mixed solution of water and ethanol, performing ultrasonic treatment, adding dopamine hydrochloride monomer and Pluronic F127, and stirring to obtain a dispersion liquid;
will [ M (Phen)3]2+Dropwise adding ethanol solution into the dispersion liquid, stirring, adjusting the pH to 7.5-10.5, stirring, centrifuging, washing, and drying to obtain a solid substance as a catalyst precursor;
carbonizing the catalyst precursor at high temperature to obtain an M-N/C catalyst;
wherein M is Fe, Co or Ni.
In a specific embodiment of the present invention, the ZIF-8 nanoparticles are Zn (NO)3)2·6H2Adding the methanol solution of O into the methanol solution of 2-methylimidazole, stirring, centrifuging, washing and drying to obtain the compound I; preferably, said Zn (NO)3)2·6H2The molar ratio of O to 2-methylimidazole is 1: 4.
In a specific embodiment of the invention, said [ M (Phen) ]3]2+The ethanol solution is prepared by mixing M (CH)3COO)2And 1, 10-phenanthroline is dissolved in ethanol; preferably, said M (CH)3COO)2The molar ratio of the compound to 1, 10-phenanthroline is 1: 3.
In a specific embodiment of the invention, the mass-to-volume ratio of the ZIF-8 nanoparticles to the mixed solution is 10mg:3 ml; preferably, the volume ratio of water to ethanol in the mixed solution is 1: 1.
In a specific embodiment of the invention, the mass ratio of the ZIF-8 nanoparticles to the dopamine hydrochloride monomer to the poloxamer F127(Pluronic F127) is 200:15: 12.
In the present inventionIn a specific embodiment, the term [ M (Phen) ]3]2+The ethanol solution has a concentration of 40-80mg ml-1(ii) a Preferably, said [ M (Phen)3]2+The ethanol solution has a concentration of 50mg ml-1. Said [ M (Phen)3]2+The volume ratio of the dripping amount of the ethanol solution to the mixed solution is 1: 100-120; preferably, said [ M (Phen)3]2+The volume ratio of the dropwise addition amount of the ethanol solution to the mixed solution is 1: 100.
In a specific embodiment of the invention, the pH is adjusted to 7.5-10.5 by adding ammonia water; preferably, the pH is adjusted to 8.5.
In a specific embodiment of the invention, the high-temperature carbonization is carried out by heating the catalyst precursor to 350 ℃ in a protective atmosphere, keeping the temperature for 2h, heating to 850-1050 ℃ and keeping the temperature for 2h, and then introducing NH when the temperature is reduced to 800 DEG C3Keeping the temperature for 2-15min, and cooling; preferably, the high-temperature carbonization is that the catalyst precursor is heated to 350 ℃ at the speed of 2 ℃ min-1 and is kept at the temperature for 2h in the protective atmosphere, then heated to 950 ℃ at the speed of 5 ℃ min-1 and is kept at the temperature for 2h, and then NH is introduced when the temperature is reduced to 800 DEG C3Keeping the temperature for 8min, and cooling. Further, the protective atmosphere is an argon atmosphere.
The dopamine is polymerized on the surface of the ZIF-8 nano-particles, and a polymer chain can adsorb and anchor the positively charged [ M (Phen) ] through strong electrostatic adsorption3]2+Form a mixture containing no [ M (Phen)3]2+Polymer-metal complexes of molecular aggregates @ MOF precursors that, after high temperature carbonization, yield M-N/C catalysts that are highly exposed dense MN4The 3D grading porous carbon-based catalyst with the active sites has higher activity. The invention adopts polydopamine for adsorbing and anchoring metal complex to coat the ZIF-8 nano-particles for the first time, so that the polydopamine can protonate 2-methylimidazole units in the ZIF-8 nano-particles, and the protonated dimethylimidazole micromolecules and Zn can be released in the carbonization process2+The obtained catalyst has a hierarchical porous structure with abundant micropores, mesopores and macropores, and the structure can promote the catalystThe exposure of single atom active sites and mass transfer process can improve the catalytic performance of the catalyst.
The invention further provides the M-N/C catalyst prepared by the method; wherein M is Fe, Co or Ni.
The Fe-N/C catalyst prepared by the invention is highly exposed dense FeN4The oxygen reduction catalyst with the active sites has a 3D hierarchical porous structure, the active sites can be fully exposed, mass transfer is enhanced, excellent oxygen reduction activity is achieved under an acidic medium, the half-wave potential can reach 0.828V, the performance of the catalyst is close to that of a commercial Pt/C catalyst, and the peak power density in a proton exchange membrane fuel cell test can reach 982mW cm-2。
The invention has the following beneficial effects:
the invention develops a novel method for preparing the catalyst by the polymer-metal complex auxiliary carbonization MOF technology for the first time, has certain universality and is suitable for preparing VIII-family non-noble metal catalysts such as Fe, Co, Ni and the like.
The method for preparing the catalyst by the polymer-metal complex assisted carbonization MOF technology has simple and feasible process and low and rich raw material cost, inhibits the formation of metal complex molecular aggregates by the simple polymer adsorption-coating MOF technology, further effectively inhibits the formation of inactive metal particles in the subsequent carbonization process, and avoids the complicated and dangerous acid etching step to obtain highly exposed dense MN4An M-N/C catalyst having an active site of (M ═ Fe, Co or Ni) has improved utilization of a metal complex type M (M ═ Fe, Co or Ni) source.
The Fe-N/C catalyst prepared by the polymer-metal complex assisted carbonization MOF technology has excellent oxygen reduction catalytic performance and stability, and shows excellent performance in the application of hydrogen-oxygen fuel cells.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a scanning electron microscope image of the Fe-N/C catalyst prepared in example 1;
FIG. 2 is a transmission electron microscope image of the Fe-N/C catalyst prepared in example 1;
FIG. 3 is a spherical aberration corrected high angle annular dark field scanning transmission electron microscope image of the Fe-N/C catalyst prepared in example 1;
FIG. 4 is an X-ray near edge absorption fine structure spectrum and radial distribution function curve of the Fe-N/C catalyst prepared in example 1;
FIG. 5 is a nitrogen-sorption-desorption isotherm curve and a pore size distribution curve of the Fe-N/C catalyst prepared in example 1;
FIG. 6 shows the Fe-N/C catalyst prepared in example 1 in 0.1M HClO4Linear sweep cyclic voltammetry of (1);
FIG. 7 is a polarization curve and a power density curve of the Fe-N/C catalyst prepared in example 1 in a proton exchange membrane fuel cell.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1 high exposure dense FeN4Preparation of high-activity Fe-N/C catalyst of site
A preparation method of a Fe-N/C catalyst comprises the following steps:
(1) 50mL of a solution containing 2.23g of Zn (NO)3)2·6H2And quickly adding the methanol solution of O into 50mL of methanol solution containing 2.46g of 2-methylimidazole, violently stirring for 5 hours at room temperature, centrifuging at a high speed to obtain a precipitate, centrifuging and washing the precipitate for 3 times by using methanol, and finally drying the precipitate in vacuum at the temperature of 60 ℃ to obtain the ZIF-8 nano particles.
(2) Dispersing 200mg of ZIF-8 nanoparticles in a mixed solution of 30ml of water and 30ml of ethanol, carrying out ultrasonic treatment for 2 hours, adding 15mg of dopamine hydrochloride monomer and 12mg of poloxamer F127(Pluronic F127), and stirring to obtain a dispersion liquid; then 0.6ml of the dispersion was added dropwiseIs 50mg ml-1Of [ Fe (Phen)3]2+Stirring the ethanol solution for 30min, adding ammonia water to adjust the pH to 8.5, contacting with air, stirring at room temperature for 24h, centrifuging at high speed to obtain precipitate, centrifuging and washing the ethanol for 3 times, and finally drying in vacuum at 60 ℃ to obtain a solid substance as a catalyst precursor.
Said [ Fe (Phen)3]2+The ethanol solution is prepared by dissolving ferrous acetate and 1, 10-phenanthroline in ethanol according to the molar ratio of 1: 3.
(3) Putting the obtained catalyst precursor into a porcelain boat, then putting the porcelain boat into a tube furnace, sealing and introducing argon, and firstly carrying out treatment at 2 ℃ for min under the argon atmosphere-1Heating to 350 deg.C, keeping the temperature for 2h, and then keeping the temperature for 5min-1Heating to 950 ℃ at the rate of (1), keeping the temperature for 2h, and introducing NH when the temperature is reduced to 800 DEG C3Preserving the heat for 8min, naturally cooling to room temperature to obtain high-exposure dense FeN4A high-activity Fe-N/C catalyst with a site.
The shapes of the prepared Fe-N/C catalyst obtained by a scanning electron microscope and a transmission electron microscope are shown in figures 1 and 2, and as can be seen from figures 1 and 2, the prepared Fe-N/C catalyst is a carbon material with a uniform concave hierarchical porous structure; an image obtained by a spherical aberration correction high-angle annular dark field scanning transmission electron microscope with atomic resolution is shown in fig. 3, and it can be seen that Fe single atoms are uniformly dispersed on the nitrogen-doped carbon material substrate.
Further, the coordination environment of the Fe atom is analyzed through X-ray absorption spectrum, which shows that the Fe atom is Fe-N in the Fe-N/C catalyst4A structure exists. The X-ray near-edge absorption fine structure spectrum is shown in FIG. 4, and it can be known that the near-edge absorption curve of the prepared Fe-N/C catalyst is close to Fe2O3The absorption curve of (a) is far away from that of the Fe foil, which shows that the valence state of Fe in the prepared Fe-N/C catalyst is close to that of Fe (III); the radial distribution function curve is shown in FIG. 4, which shows that the prepared Fe-N/C catalyst contains no Fe-Fe bonds and only Fe-N bonds, and indicates that the Fe element in the prepared catalyst is only Fe-N4The structure of (1) exists.
Further, a nitrogen-adsorption-desorption isothermal curve and a pore size distribution curve of the prepared Fe-N/C catalyst are obtained through a nitrogen isothermal adsorption-desorption test and are shown in fig. 5, so that the prepared Fe-N/C catalyst is a hierarchical porous catalyst material containing abundant micropores, mesopores and macropores, and the hierarchical porous structure is favorable for increasing the exposure of active sites and improving the mass transfer process, thereby improving the catalytic performance of the material.
The oxygen reduction performance of the Fe-N/C catalyst prepared above and the commercial Pt/C catalyst were further measured at 0.1M HClO using a rotating disk electrode, respectively4The prepared Fe-N/C catalyst is obtained in 0.1M HClO4The linear sweep cyclic voltammogram of (1) is shown in FIG. 6, and it can be seen that the half-wave potential of the prepared Fe-N/C catalyst can reach 0.828V (vs. RHE), which is close to that of the commercial Pt/C catalyst.
Further applying the prepared Fe-N/C catalyst to H2-O2The proton exchange membrane fuel cell, the polarization curve and the power density curve in the proton exchange membrane fuel cell are shown in figure 7, and the peak power density of the prepared Fe-N/C catalyst can reach 982mW/cm2。
Example 2 high-exposure dense CoN4Preparation of high-activity Co-N/C catalyst of site
A preparation method of a high-activity Co-N/C catalyst comprises the following steps:
(1) 50mL of a solution containing 2.23g of Zn (NO)3)2·6H2And quickly adding the methanol solution of O into 50mL of methanol solution containing 2.46g of 2-methylimidazole, violently stirring for 5 hours at room temperature, centrifuging at a high speed to obtain a precipitate, centrifuging and washing the precipitate for 3 times by using methanol, and finally drying the precipitate in vacuum at the temperature of 60 ℃ to obtain the ZIF-8 nano particles.
(2) Dispersing 200mg of ZIF-8 nanoparticles in a mixed solution of 30ml of water and 30ml of ethanol, carrying out ultrasonic treatment for 2 hours, adding 15mg of dopamine hydrochloride monomer and 12mg of Pluronic F127, and stirring to obtain a dispersion solution; then 0.6ml of 50mg ml of a solution having a concentration of 0.6ml is added dropwise to the dispersion-1Of (Co (Phen)3]2+Stirring the ethanol solution for 30min, adding ammonia water to adjust the pH to 8.5, contacting with air, stirring at room temperature for 24h, centrifuging at high speed to obtain precipitate, centrifuging and washing the ethanol for 3 times, and finally drying in vacuum at 60 ℃ to obtain a solid substance as a catalyst precursor.
Said [ Co (Phen)3]2+The ethanol solution is prepared by dissolving cobalt acetate and 1, 10-phenanthroline in ethanol according to the molar ratio of 1: 3.
(3) Putting the obtained catalyst precursor into a porcelain boat, then putting the porcelain boat into a tube furnace, sealing and introducing argon, and firstly carrying out treatment at 2 ℃ for min under the argon atmosphere-1Heating to 350 deg.C at a rate of 2 hr, and maintaining at 5 deg.C for 5min-1Heating to 950 ℃ at the rate of (1), keeping the temperature for 2h, and introducing NH when the temperature is reduced to 800 DEG C3Preserving the temperature for 8min, naturally cooling to room temperature to obtain high-exposure dense CoN4A high-activity Co-N/C catalyst with a site.
Example 3 high exposure dense NiN4Preparation of high-activity Ni-N/C catalyst of site
A preparation method of a high-activity Ni-N/C catalyst comprises the following steps:
(1) 50mL of a solution containing 2.23g of Zn (NO)3)2·6H2And quickly adding the methanol solution of O into 50mL of methanol solution containing 2.46g of 2-methylimidazole, violently stirring for 5 hours at room temperature, centrifuging at a high speed to obtain a precipitate, centrifuging and washing the precipitate for 3 times by using methanol, and finally drying the precipitate in vacuum at the temperature of 60 ℃ to obtain the ZIF-8 nano particles.
(2) Dispersing 200mg of ZIF-8 nano particles in a mixed solution of 30ml of water and 30ml of ethanol, carrying out ultrasonic treatment for 2 hours, adding 15mg of dopamine hydrochloride monomer and 12mg of Pluronic F127, and stirring to obtain a dispersion liquid; then 0.6ml of 50mg ml of a solution having a concentration of 0.6ml is added dropwise to the dispersion-1Of (A) and (Phen)3]2+Stirring the ethanol solution for 30min, adding ammonia water to adjust the pH to 8.5, contacting with air, stirring at room temperature for 24h, centrifuging at high speed to obtain precipitate, centrifuging and washing the ethanol for 3 times, and finally drying in vacuum at 60 ℃ to obtain a solid substance as a catalyst precursor.
Said [ Ni (Phen)3]2+The ethanol solution is prepared by dissolving nickel acetate and 1, 10-phenanthroline in ethanol according to the molar ratio of 1: 3.
(3) Putting the obtained catalyst precursor into a porcelain boat, then putting the porcelain boat into a tube furnace, sealing and introducing argon, and firstly carrying out treatment at 2 ℃ for min under the argon atmosphere-1Heating to 350 deg.C at a rate of 2 hr, and maintaining at 5 deg.C for 5min-1Heating to 950 ℃ at the rate of (1), keeping the temperature for 2h, and introducing NH when the temperature is reduced to 800 DEG C3Keeping the temperature for 8min, naturally cooling to room temperature to obtain high-exposure dense NiN4High activity Ni-N/C catalyst of site.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. A method for preparing a catalyst by a polymer-metal complex assisted carbonization MOF technology is characterized by comprising the following steps:
dispersing ZIF-8 nanoparticles in a mixed solution of water and ethanol, performing ultrasonic treatment, adding a dopamine hydrochloride monomer and Pluronic F127, and stirring to obtain a dispersion solution;
will [ M (Phen)3]2+Dropwise adding ethanol solution into the dispersion liquid, stirring, adjusting the pH to 7.5-10.5, stirring, centrifuging, washing, and drying to obtain a solid substance as a catalyst precursor;
carbonizing the catalyst precursor at high temperature to obtain an M-N/C catalyst;
wherein M is Fe, Co or Ni.
2. The method of claim 1, wherein the ratio of the ZIF-8 nanoparticles to the mixed liquor is 10mg to 3ml by mass.
3. The method according to claim 1, wherein the volume ratio of water to ethanol in the mixed solution is 1: 1.
4. The method of claim 1, wherein the mass ratio of the ZIF-8 nanoparticles, dopamine hydrochloride monomer, Pluronic F127 is 200:15: 12.
5. The method of claim 1, wherein [ M (Phen)3]2+The ethanol solution has a concentration of 40-80mg ml-1(ii) a Preferably, said [ M (Phen)3]2+The ethanol solution has a concentration of 50mg ml-1。
6. The method of claim 1, wherein [ M (Phen)3]2+The volume ratio of the dripping amount of the ethanol solution to the mixed solution is 1: 100-120; preferably, said [ M (Phen)3]2+The volume ratio of the dropwise addition amount of the ethanol solution to the mixed solution is 1: 100.
7. The method according to claim 1, wherein the high-temperature carbonization comprises the steps of heating the catalyst precursor to 350 ℃ in a protective atmosphere, keeping the temperature for 2h, heating to 850-1050 ℃ and keeping the temperature for 2h, and then introducing NH when the temperature is reduced to 800 ℃3Keeping the temperature for 2-15min, and cooling; preferably, the protective atmosphere is an argon atmosphere.
8. The method of claim 1, wherein the ZIF-8 nanoparticles are Zn (NO)3)2·6H2Adding the methanol solution of O into the methanol solution of 2-methylimidazole, stirring, centrifuging, washing and drying to obtain the compound I; preferably, said Zn (NO)3)2·6H2The molar ratio of O to 2-methylimidazole is 1: 4.
9. The method of claim 1, wherein [ M (Phen)3]2+The ethanol solution is prepared by mixing M (CH)3COO)2And 1, 10-phenanthroline is dissolved in ethanol; preferably, said M (CH)3COO)2The molar ratio of the compound to 1, 10-phenanthroline is 1: 3.
10. An M-N/C catalyst prepared by the process of any one of claims 1 to 9; wherein M is Fe, Co or Ni.
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