CN113690452B - Method for preparing catalyst by polymer-metal complex assisted carbonization MOF technology and catalyst obtained by same - Google Patents
Method for preparing catalyst by polymer-metal complex assisted carbonization MOF technology and catalyst obtained by same Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000003763 carbonization Methods 0.000 title claims abstract description 29
- 238000005516 engineering process Methods 0.000 title claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000243 solution Substances 0.000 claims abstract description 29
- 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
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 24
- 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 19
- 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
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 5
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 238000001816 cooling Methods 0.000 claims description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 8
- 229920001992 poloxamer 407 Polymers 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 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 8
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 description 9
- 239000000446 fuel Substances 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 102000020897 Formins Human genes 0.000 description 6
- 108091022623 Formins Proteins 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 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
- 239000012528 membrane Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910020676 Co—N Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 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
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005315 distribution function Methods 0.000 description 2
- 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
- 230000010287 polarization Effects 0.000 description 2
- 229920001983 poloxamer Polymers 0.000 description 2
- 229960000502 poloxamer Drugs 0.000 description 2
- 229920001690 polydopamine Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000001228 spectrum 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
- 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
- 239000013590 bulk material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 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
- 150000001875 compounds Chemical class 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing a catalyst by a polymer-metal complex assisted carbonization (MOF) technology and the catalyst obtained by the method. The present invention first discloses a method for preparing a catalyst, comprising: dispersing ZIF-8 nano particles in a mixed solution of water and ethanol, adding dopamine hydrochloride monomer and PluronicF127, and stirring to obtain a dispersion; will [ M (Phen) 3 ] 2+ Dripping ethanol solution into the dispersion liquid, stirring, regulating the pH to 7.5-10.5, stirring, centrifuging, washing and drying to obtain a solid substance serving 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 easy to implement, and the highly exposed dense FeN is obtained 4 The active site catalyst has excellent oxygen reduction catalytic performance.
Description
Technical Field
The present invention relates to the field of monoatomic electrocatalysis. And more particularly to a method of preparing a catalyst by polymer-metal complex assisted carbonization MOF technology and the resulting catalyst.
Background
With the progress of human society, the global energy consumption is rapidly increased, and the problems of energy crisis, environmental pollution, climate change and the like are increasingly outstanding, so that the development of clean energy technology which is known as zero pollution and high energy conversion efficiency is particularly important. The Proton Exchange Membrane Fuel Cell (PEMFC) can directly convert chemical energy into electric energy through electrocatalytic reaction, has the advantages of low working temperature, high power density, quick start and the like, and is widely researched by scientific researchers. However, the cathode Oxygen Reduction Reaction (ORR) kinetics of PEMFCs are slow, and commercial Pt/C containing noble metal Pt is required as a catalyst, and the expensive catalyst price restricts the commercialization process of fuel cells. In order to make fuel cells widely used as early as possible, the development of low-cost non-noble metal catalysts that can replace commercial Pt/C is a research hotspot in the current fuel cell field.
Currently, atomically dispersed Fe-N/C non-noble metal catalysts are usedIs considered to be one of the most promising candidates for replacing commercial platinum carbon catalysts. Comprising FeN 4 Active site Fe-N/C monoatomic catalysts, while highly active, still have a distance to their performance compared to commercial Pt/C. The common performance optimization method at present is to increase the metal atom content (namely FeN 4 Active site concentration), however, high temperature pyrolysis is generally adopted in the method for synthesizing the Fe-N/C catalyst, and increasing the density of active sites only by increasing the concentration of a metal Fe source often results in a large amount of inactive Fe nanoparticles, so that the utilization rate of the Fe source is reduced, and a complicated acid etching step is required to remove the Fe nanoparticles to obtain the monoatomic catalyst. On the other hand, the catalyst with reasonable pore structure can fully expose FeN 4 Active site, can increase FeN 4 Utilization of active sites.
Thus, there is a great need for a practical and easy method of producing dense FeN with high exposure 4 High active catalyst of active site.
Disclosure of Invention
An object of the present invention is to provide a method for preparing a catalyst by polymer-metal complex assisted carbonization of metal framework compounds (MOF) technology, which is simple and easy to implement with low raw material cost.
Another object of the present invention is to provide a monoatomic Fe-N/C catalyst obtained by the above process, which has a highly exposed dense FeN 4 Active sites exhibit excellent catalytic performance in the cathodic oxygen reduction reaction of hydrogen-oxygen fuel cells.
To achieve the above object, the present invention provides a method for preparing a catalyst by a polymer-metal complex assisted carbonized metal framework (MOF) technique, comprising the steps of:
dispersing ZIF-8 nano particles in a mixed solution of water and ethanol, adding dopamine hydrochloride monomer and Pluronic F127, and stirring to obtain a dispersion;
will [ M (Phen) 3 ] 2+ Dripping ethanol solution into the dispersion liquid, stirring, regulating pH to 7.5-10.5, stirring, centrifuging, washing, and drying to obtain solidThe bulk material acts 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 prepared by mixing Zn (NO 3 ) 2 ·6H 2 Adding the methanol solution of O into the methanol solution of 2-methylimidazole, stirring, centrifuging, washing and drying to obtain the catalyst; preferably, the Zn (NO 3 ) 2 ·6H 2 The molar ratio of O to 2-methylimidazole was 1:4.
In a specific embodiment of the present invention, the [ M (Phen) 3 ] 2+ The ethanol solution is prepared by mixing M (CH) 3 COO) 2 And 1, 10-phenanthroline is dissolved in ethanol to obtain the preparation; preferably, the M (CH 3 COO) 2 The molar ratio of the catalyst to the 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 10 mg/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 ZIF-8 nanoparticle, the dopamine hydrochloride monomer and poloxamer F127 (Pluronic F127) have a mass ratio of 200:15:12.
In a specific embodiment of the present invention, the [ M (Phen) 3 ] 2+ The concentration of ethanol solution is 40-80mg ml -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, said [ M (Phen) 3 ] 2+ The concentration of the ethanol solution is 50mg ml -1 . Said [ M (Phen) 3 ] 2+ The volume ratio of the dropping amount of the ethanol solution to the mixed solution is 1:100-120; preferably, said [ M (Phen) 3 ] 2+ The volume ratio of the dropping 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 performed by heating the catalyst precursor to a temperature in a protective atmospherePreserving heat for 2h at 350 ℃, then preserving heat for 2h at 850-1050 ℃, and then introducing NH when cooling to 800 DEG C 3 Preserving heat for 2-15min, and cooling; preferably, the high temperature carbonization is to heat the catalyst precursor to 350 ℃ at a rate of 2 ℃ min < -1 > in a protective atmosphere for 2 hours, heat to 950 ℃ at a rate of 5 ℃ min < -1 > for 2 hours, and then introduce NH when cooling to 800 DEG C 3 Preserving heat for 8min, and cooling. Further, the protective atmosphere is an argon atmosphere.
The dopamine of the invention is polymerized on the surface of ZIF-8 nano particles, and the polymer chain can adsorb and anchor the positively charged [ M (Phen) through strong electrostatic adsorption 3 ] 2+ To form a product free of [ M (Phen) 3 ] 2+ Polymer-metal complex @ MOF precursors of molecular aggregates which, after carbonization at high temperature, give M-N/C catalysts which are highly exposed dense MNs 4 The 3D hierarchical porous carbon-based catalyst with active sites has higher activity. According to the invention, polydopamine for adsorbing and anchoring metal complex is adopted for the first time to coat ZIF-8 nano particles, 2-methylimidazole units in the ZIF-8 nano particles can be protonated due to polydopamine, and protonated dimethyl imidazole micromolecules and Zn can be released in the carbonization process 2+ The catalyst has rich hierarchical porous structure of micropores, mesopores and macropores, and the structure can promote the exposure and mass transfer process of single atom active sites in the catalyst, so that the catalytic performance of the catalyst can be improved.
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 a highly exposed dense FeN 4 The active site oxygen reduction catalyst has a 3D hierarchical porous structure, the active site can be fully exposed, mass transfer is enhanced, the active site oxygen reduction catalyst has excellent oxygen reduction activity under an acidic medium, half-wave potential can reach 0.828V, the catalyst performance is close to that of commercial Pt/C, and the peak power density in a proton exchange membrane fuel cell test can reach 982mW cm -2 。
The beneficial effects of the invention are as follows:
the invention develops a novel method for preparing the catalyst by using the polymer-metal complex assisted carbonization MOF technology for the first time, has certain universality and is suitable for preparing the catalyst of VIII non-noble metal elements such as Fe, co, ni and the like.
The method for preparing the catalyst by using the polymer-metal complex assisted carbonization MOF technology has the advantages of simple and easy process, low and abundant raw material cost, and can inhibit the formation of metal complex molecular aggregates by using a simple polymer adsorption-coating MOF process, further effectively inhibit the formation of inactive metal particles in the subsequent carbonization process, avoid complicated and dangerous acid etching steps and obtain the highly exposed dense MN 4 The M-N/C catalyst of (m=fe, co or Ni) active site improves the utilization of the metal complex 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 oxyhydrogen fuel cell application.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the 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 correcting 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 side absorption fine structure spectrum and a radial distribution function curve of the Fe-N/C catalyst prepared in example 1;
FIG. 5 is a nitrogen-adsorption/desorption isothermal 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 at 0.1M HClO 4 A linear sweep cyclic voltammogram of (a);
FIG. 7 is a graph showing the polarization and power density curves 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 present invention, the present invention will be further described with reference to preferred embodiments and the accompanying drawings. Like parts in the drawings 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 that this invention is not limited to the details given herein.
EXAMPLE 1 high exposure dense FeN 4 Preparation of site-directed high activity Fe-N/C catalysts
A preparation method of an Fe-N/C catalyst comprises the following steps:
(1) 50mL of the mixture containing 2.23g of Zn (NO) 3 ) 2 ·6H 2 And (3) rapidly adding the methanol solution of O into 50mL of methanol solution containing 2.46g of 2-methylimidazole, stirring vigorously at room temperature for 5h, centrifuging at a high speed to obtain a precipitate, centrifuging the methanol, washing for 3 times, and finally drying in vacuum at 60 ℃ to obtain 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 poloxamer F127 (Pluronic F127), and stirring to obtain a dispersion; then 0.6ml of 50mg ml of the dispersion was added dropwise -1 [ Fe (Phen) 3 ] 2+ Stirring the ethanol solution for 30min, adding ammonia water to adjust the pH value to 8.5, contacting air, stirring at room temperature for 24h, centrifuging at high speed to obtain a precipitate, centrifuging the precipitate with ethanol, washing for 3 times, and finally drying in vacuum at 60 ℃ to obtain a solid substance serving as a catalyst precursor.
The [ Fe (Phen) 3 ] 2+ The ethanol solution is prepared by dissolving ferrous acetate and 1, 10-phenanthroline in ethanol according to a molar ratio of 1:3.
(3) Putting the obtained catalyst precursor into a porcelain boat, then putting into a tube furnace, sealing and introducing argon, and under the argon atmosphere, firstly taking the temperature of 2 ℃ for min -1 Is heated to 350 ℃ for 2h and then is heated to 5 ℃ for min -1 Heating to 950 ℃ for 2h, cooling to 800 ℃ and introducing NH 3 Thermal insulationCooling naturally to room temperature for 8min to obtain high exposure density FeN 4 A high activity Fe-N/C catalyst of the locus.
The morphology of the prepared Fe-N/C catalyst is shown in figures 1 and 2 by a scanning electron microscope and a transmission electron microscope, and as can be seen from figures 1 and 2, the prepared Fe-N/C catalyst is a uniform carbon material with a concave hierarchical porous structure; the image obtained by means of an atomic-resolution spherical aberration correcting high-angle annular dark field scanning transmission electron microscope is shown in fig. 3, and it can be seen that Fe monoatoms are uniformly dispersed on the nitrogen-doped carbon material substrate.
Further analyzes the coordination environment of Fe atoms by X-ray absorption spectrum, which shows that the Fe atoms take Fe-N in the Fe-N/C catalyst 4 The structure exists. As shown in FIG. 4, the spectrum of the fine structure of the near-edge absorption of X-ray shows that the near-edge absorption curve of the prepared Fe-N/C catalyst is close to that of Fe 2 O 3 Is far from the absorption curve of the Fe foil, indicating that the valence state of Fe in the prepared Fe-N/C catalyst is close to that of Fe (III); as shown in FIG. 4, the radial distribution function curve shows that the prepared Fe-N/C catalyst contains no Fe-Fe bond and only Fe-N bond, indicating that the Fe element in the prepared catalyst is only Fe-N 4 Is present.
The nitrogen-adsorption-desorption isothermal curve and the pore size distribution curve of the prepared Fe-N/C catalyst are shown in figure 5, and the prepared Fe-N/C catalyst is a hierarchical porous catalyst material containing abundant micropores, mesopores and macropores, and the hierarchical porous structure is beneficial to increasing the exposure of active sites and improving the mass transfer process, so that the catalytic performance of the material is improved.
Further, the oxygen reduction properties of the Fe-N/C catalyst and the commercial Pt/C catalyst prepared as described above were respectively measured at 0.1M HClO using a rotating disk electrode 4 The characterization of the catalyst to obtain the prepared Fe-N/C catalyst in 0.1M HClO 4 The linear sweep cyclic voltammogram of (C) 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 using the Fe-N/C catalyst prepared by the methodIn H 2 -O 2 The polarization curve and the power density curve obtained in the proton exchange membrane fuel cell are shown in FIG. 7, and it is known that the peak power density of the prepared Fe-N/C catalyst can reach 982mW/cm 2 。
Example 2 high exposure dense CoN 4 Preparation of site-directed high activity Co-N/C catalysts
A preparation method of a high-activity Co-N/C catalyst comprises the following steps:
(1) 50mL of the mixture containing 2.23g of Zn (NO) 3 ) 2 ·6H 2 And (3) rapidly adding the methanol solution of O into 50mL of methanol solution containing 2.46g of 2-methylimidazole, stirring vigorously at room temperature for 5h, centrifuging at a high speed to obtain a precipitate, centrifuging the methanol, washing for 3 times, and finally drying in vacuum at 60 ℃ to obtain 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 Pluronic F127, and stirring to obtain a dispersion; then 0.6ml of 50mg ml of the dispersion was added dropwise -1 [ Co (Phen) 3 ] 2+ Stirring the ethanol solution for 30min, adding ammonia water to adjust the pH value to 8.5, contacting air, stirring at room temperature for 24h, centrifuging at high speed to obtain a precipitate, centrifuging the precipitate with ethanol, washing for 3 times, and finally drying in vacuum at 60 ℃ to obtain a solid substance serving 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 a molar ratio of 1:3.
(3) Putting the obtained catalyst precursor into a porcelain boat, then putting into a tube furnace, sealing and introducing argon, and under the argon atmosphere, firstly taking the temperature of 2 ℃ for min -1 Is heated to 350 ℃ and is kept warm for 2 hours at the rate of 5 ℃ for min -1 Heating to 950 ℃ for 2h, cooling to 800 ℃ and introducing NH 3 Preserving heat for 8min, naturally cooling to room temperature to obtain high exposure density CoN 4 A high activity Co-N/C catalyst of the site.
Example 3 high exposure Density NiN 4 Preparation of site-directed high activity Ni-N/C catalysts
A preparation method of a high-activity Ni-N/C catalyst comprises the following steps:
(1) 50mL of the mixture containing 2.23g of Zn (NO) 3 ) 2 ·6H 2 And (3) rapidly adding the methanol solution of O into 50mL of methanol solution containing 2.46g of 2-methylimidazole, stirring vigorously at room temperature for 5h, centrifuging at a high speed to obtain a precipitate, centrifuging the methanol, washing for 3 times, and finally drying in vacuum at 60 ℃ to obtain 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 Pluronic F127, and stirring to obtain a dispersion; then 0.6ml of 50mg ml of the dispersion was added dropwise -1 [ Ni (Phen) 3 ] 2+ Stirring the ethanol solution for 30min, adding ammonia water to adjust the pH value to 8.5, contacting air, stirring at room temperature for 24h, centrifuging at high speed to obtain a precipitate, centrifuging the precipitate with ethanol, washing for 3 times, and finally drying in vacuum at 60 ℃ to obtain a solid substance serving 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 a molar ratio of 1:3.
(3) Putting the obtained catalyst precursor into a porcelain boat, then putting into a tube furnace, sealing and introducing argon, and under the argon atmosphere, firstly taking the temperature of 2 ℃ for min -1 Is heated to 350 ℃ and is kept warm for 2 hours at the rate of 5 ℃ for min -1 Heating to 950 ℃ for 2h, cooling to 800 ℃ and introducing NH 3 Preserving heat for 8min, naturally cooling to room temperature to obtain high exposure density NiN 4 A high activity Ni-N/C catalyst of site.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (15)
1. A method for preparing a catalyst by polymer-metal complex assisted carbonization, MOF, technique, comprising the steps of:
dispersing ZIF-8 nano particles in a mixed solution of water and ethanol, adding dopamine hydrochloride monomer and Pluronic F127, and stirring to obtain a dispersion;
will [ M (Phen) 3 ] 2+ Dripping ethanol solution into the dispersion liquid, stirring, regulating the pH to 7.5-10.5, stirring, centrifuging, washing and drying to obtain a solid substance serving 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 preparing a catalyst by polymer-metal complex assisted carbonization, MOF, technique according to claim 1, characterized in that the mass to volume ratio of ZIF-8 nanoparticles to the mixed liquor is 10mg:3ml.
3. The method of preparing a catalyst by polymer-metal complex assisted carbonization MOF technology according to claim 1, characterized in that the volume ratio of water and ethanol in the mixed liquor is 1:1.
4. The method for preparing a catalyst by polymer-metal complex assisted carbonization MOF technology according to claim 1, wherein the mass ratio of ZIF-8 nanoparticles, dopamine hydrochloride monomer, pluronic F127 is 200:15:12.
5. The method for preparing a catalyst by polymer-metal complex assisted carbonization MOF technique according to claim 1, wherein the [ M (Phen) 3 ] 2+ The concentration of ethanol solution is 40-80mg ml -1 。
6. The method for preparing a catalyst by polymer-metal complex assisted carbonization MOF technique according to claim 5, which is characterized in thatCharacterized in that said [ M (Phen) 3 ] 2+ The concentration of the ethanol solution is 50mg ml -1 。
7. The method for preparing a catalyst by polymer-metal complex assisted carbonization MOF technique according to claim 1, wherein the [ M (Phen) 3 ] 2+ The volume ratio of the dropping amount of the ethanol solution to the mixed solution is 1:100-120.
8. The method for preparing a catalyst by polymer-metal complex assisted carbonization MOF technique according to claim 7, wherein [ M (Phen) ] 3 ] 2+ The volume ratio of the dropping amount of the ethanol solution to the mixed solution is 1:100.
9. The method for preparing a catalyst by a polymer-metal complex assisted carbonization (MOF) technology according to claim 1, wherein the high-temperature carbonization is carried out by heating the catalyst precursor to 350 ℃ for 2 hours, heating to 850-1050 ℃ for 2 hours, and then cooling to 800 ℃ for introducing NH 3 Preserving heat for 2-15min, and cooling.
10. The method of preparing a catalyst by polymer-metal complex assisted carbonization, MOF, technique according to claim 9, characterized in that the protective atmosphere is an argon atmosphere.
11. The method of preparing a catalyst by polymer-metal complex assisted carbonization MOF technology according to claim 1, characterized in that the ZIF-8 nanoparticle is a catalyst prepared by adding Zn (NO 3 ) 2 ·6H 2 Adding the methanol solution of O into the methanol solution of 2-methylimidazole, stirring, centrifuging, washing and drying to obtain the O-methylimidazole.
12. The method of preparing a catalyst by polymer-metal complex assisted carbonization MOF technique according to claim 11, characterized in that Zn (NO 3 ) 2 ·6H 2 The molar ratio of O to 2-methylimidazole was 1:4.
13. The method for preparing a catalyst by polymer-metal complex assisted carbonization MOF technique according to claim 1, wherein the [ M (Phen) 3 ] 2+ The ethanol solution is prepared by mixing M (CH) 3 COO) 2 And 1, 10-phenanthroline is dissolved in ethanol.
14. The method of preparing a catalyst by polymer-metal complex assisted carbonization, MOF, technique according to claim 13, characterized in that M (CH 3 COO) 2 The molar ratio of the catalyst to the 1, 10-phenanthroline is 1:3.
15. An M-N/C catalyst prepared by the method of preparing a catalyst according to any one of claims 1-14 by polymer-metal complex assisted carbonization MOF technology; wherein M is Fe, co or Ni.
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