CN114784301B - Non-noble metal cathode catalyst material and preparation method and application thereof - Google Patents
Non-noble metal cathode catalyst material and preparation method and application thereof Download PDFInfo
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- CN114784301B CN114784301B CN202111567132.9A CN202111567132A CN114784301B CN 114784301 B CN114784301 B CN 114784301B CN 202111567132 A CN202111567132 A CN 202111567132A CN 114784301 B CN114784301 B CN 114784301B
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- 239000000463 material Substances 0.000 title claims abstract description 96
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 47
- 150000003624 transition metals Chemical class 0.000 claims abstract description 33
- 238000000197 pyrolysis Methods 0.000 claims abstract description 25
- 238000000498 ball milling Methods 0.000 claims abstract description 23
- 239000000446 fuel Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 10
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 58
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 45
- 239000013153 zeolitic imidazolate framework Substances 0.000 claims description 37
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 37
- 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 description 37
- 238000001354 calcination Methods 0.000 claims description 32
- -1 transition metal salt Chemical class 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 22
- 239000012621 metal-organic framework Substances 0.000 claims description 21
- 229910021536 Zeolite Inorganic materials 0.000 claims description 16
- 239000010457 zeolite Substances 0.000 claims description 16
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000005416 organic matter Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 4
- 238000004945 emulsification Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 229960003638 dopamine Drugs 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 7
- 239000013384 organic framework Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 21
- 238000004502 linear sweep voltammetry Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000013522 chelant Substances 0.000 description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000011324 bead Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 238000005232 molecular self-assembly Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- WDLZFIOOXUEMKS-UHFFFAOYSA-N N1=CC=CC2=CC=C3C=CC=NC3=C12.[N] Chemical compound N1=CC=CC2=CC=C3C=CC=NC3=C12.[N] WDLZFIOOXUEMKS-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- 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
- 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)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a non-noble metal cathode catalyst material, a preparation method and application thereof. The method comprises preparing a zeolitic imidazolate metallo-organic framework polymer; ball milling and mixing; self-assembling molecules and performing two-step pyrolysis. The application of the catalyst prepared by the method in fuel cells is also disclosed. The method can prepare the transition metal doped nitrogen-carbon material with single atomic distribution in batch.
Description
Technical Field
The invention relates to a non-noble metal cathode catalyst material, a preparation method and application thereof, in particular to a preparation method for preparing a single-atom-distribution transition metal doped nitrogen-carbon material for a fuel cell in batches.
Background
In the large background of the carbon peaks, the use of clean energy without carbon emissions is called for worldwide. Hydrogen energy has been attracting attention because of its zero emission, and proton exchange membrane fuel cells have shown great potential for use in many fields (transportation means, aerospace and military equipment, etc.) because they are portable devices that directly convert hydrogen energy into electrical energy without undergoing carnot cycles. However, the electrocatalyst used in the electrode of the proton exchange membrane fuel cell widely used commercially today is mainly Pt/C material, and development of the electrocatalyst material containing no noble metal Pt is one of the final solutions because the extreme scarcity of Pt resources hinders the commercialization development.
Among them, the transition metal doped nitrogen-carbon material has been proved by researchers to be a reliable electrocatalyst material, and the activity of the material is particularly remarkable in oxygen reduction. In this regard, researchers have developed a number of studies, particularly on monoatomically dispersed transition metal doped nitrogen carbon materials. However, the current preparation methods of the nitrogen-carbon catalyst material doped with the monoatomic non-noble metal are generally very complex, and can only be prepared in experimental magnitude, so that the practical production significance and the economical efficiency are low. Therefore, the development of a simple and portable transition metal doped nitrogen-carbon material capable of preparing single-atom distribution in batches is of great significance.
Disclosure of Invention
The invention firstly provides a preparation method of a non-noble metal cathode catalyst material, which can prepare transition metal doped nitrogen-carbon materials with single atom distribution in batches.
A method of preparing a non-noble metal cathode catalyst material comprising:
Mixing transition metal salt, nitrogen-containing organic matters and zeolite imidazole ester metal organic framework material ZIF, and ball milling to obtain uniform powder mixture M/ZIF containing transition metal;
Dispersing a powder mixture M/ZIF containing transition metal in a solvent to coordinate the transition metal ions, the nitrogen-containing organic matters and the zeolite imidazole ester metal organic framework material ZIF; then removing transition metal ions and nitrogenous organic matters which are not coordinated; drying to obtain an M-ZIF precursor containing transition metal monoatoms which are uniformly distributed;
and calcining and pyrolyzing the M-ZIF precursor containing the single atoms of the transition metal in two steps to obtain the single-atom-distributed transition metal-doped nitrogen-carbon material, namely the non-noble metal cathode catalyst material.
The invention researches that the traditional liquid phase adsorption method is mainly used for preparing the transition metal doped ZIF-8 mixture, so that the adsorption quantity of the transition metal is greatly dependent on the specific surface area of the ZIF-8, the ZIF-8 prepared at present is required to have very small particle size, the preparation of the ZIF-8 with small particle size needs to be carried out with very dilute Zn (NO 3)2·6H2 O methanol solution, thereby greatly increasing the consumption of methanol and increasing the technical difficulty of mass production, the transition metal doped ZIF-8 mixture in the invention has low requirement on the particle size of the ZIF-8 because the transition metal in the material of the invention is distributed in a mode of simple physical adsorption distribution, and more forms chelate with nitrogen-containing organic matters (phenanthroline) in a coordination mode, so that the ZIF-8 is uniformly distributed or coordinated on a ZIF-8 framework structure in the process of molecular reassembly, and in addition, the average size of micropores in the organic framework of the ZIF-8 isTypical particles such as phenanthroline iron chelate have an average size ofTherefore, the phenanthroline iron chelate molecules are difficult to enter into the inner frame structure of the ZIF-8, and most of the phenanthroline iron chelate molecules are only attached to the surface layer of the ZIF-8 frame material in an adsorption mode. Therefore, the ball milling introduced in the invention can completely pulverize ZIF-8 regular dodecahedron frames and generate a large number of defects, so that the composite material rich in monodisperse transition metals in the surface layer and the bulk phase can be obtained during subsequent molecular self-assembly.
Further, the zeolitic imidazolate metal organic framework material ZIF may be selected from the group consisting of ZIF-8, ZIF-67.
In the invention, the zeolite imidazole ester metal organic framework material ZIF can be prepared by adopting a conventional method in the field.
In some examples, the preparation method of the zeolite imidazole ester metal organic framework material ZIF comprises the following steps: dissolving zinc salt in methanol solvent, adding imidazole monomer (such as 2-methylimidazole) after complete dissolution, continuing stirring until the solution is milky, standing for emulsification, and finally centrifuging, washing and drying to obtain the zeolite imidazole ester metal organic framework material ZIF-8.
Further, the mass ratio of the ball materials during ball milling is 100-10:1.
Further, the rotational speed of the ball milling is 200-1000 rpm, and the ball milling time is 1-24 h.
It was found that the ZIF-8 material framework structure can be completely pulverized by ball milling under the above conditions.
Further, the mass ratio of the transition metal salt, the nitrogen-containing organic matter and the zeolite imidazole ester metal organic framework material ZIF is 1 (5-20): (20-100), for example, 1:10:40.
Further, the transition metal is one or more of Fe, cu, co, ni and Mn. The transition metal salt can be selected from one or more of chloride, nitrate, sulfate, acetate, citrate and acetylacetone compound of the above transition metal.
Further, the nitrogen-containing organic matter is one or more of phenanthroline, acetamide, ethylamine, pyrrole, aniline, ethylenediamine, dopamine, dicyandiamide, urea, butyronitrile and melamine, and preferably is phenanthroline.
As a preferred embodiment of the present invention, the transition metal salt is one or more of chloride, nitrate, sulfate, acetate, citrate, acetylacetonate of Fe, preferably acetate (iron (II) acetate); the nitrogenous organic matter is phenanthroline. The Fe chelate of the phenanthroline formed by the transition metal salt (Fe, co, ni and Mn) and the phenanthroline can ensure the original catalytic performance under the condition of increasing the particle size and the yield of the prepared non-noble metal cathode catalyst material.
Further, the solvent for dispersing the transition metal-containing powder mixture M/ZIF may be selected from alcohol/water mixed solvents, wherein the volume ratio of alcohol/water is 10 to 1:1. The alcohol may be methanol or ethanol.
Further, the method of removing the uncomplexed transition metal ions and nitrogen-containing organic matter may be centrifugation and/or washing.
Further, in the two-step calcination pyrolysis, the temperature range of the first-step calcination pyrolysis is 200-600 ℃; the temperature range of the second step of calcination pyrolysis is 900-1100 ℃.
The inventor researches and discovers that the first step of calcination pyrolysis treatment is adopted under the low-temperature condition, so that bound water and some unstable organic monomers in the composite material can be removed, and meanwhile, the coordination strength of transition metal elements and nitrogen elements is enhanced, so that the distribution of single atoms is stabilized. And then carrying out pyrolysis treatment by adopting a second step of calcination and pyrolysis treatment under the high-temperature condition, and carrying out pyrolysis and carbonization on the compound, thereby preparing the high-stability transition metal doped nitrogen-carbon material. In particular, by adopting the two-step calcination pyrolysis treatment, the catalyst material can still maintain better catalytic performance under the condition that the particle size of the prepared non-noble metal cathode catalyst material is increased, so that the yield can be increased.
In some examples, the first step of calcination pyrolysis can be for a period of 1 to 10 hours, such as 2 hours.
In some examples, the time for the second step calcination pyrolysis may be from 1 to 10 hours, for example 1 hour.
In some examples, the first step of calcination pyrolysis is at 400 ℃ for 2 hours; the pyrolysis temperature of the second calcination is 1000 ℃ and the time is 1h.
In some examples, the method of preparing the non-noble metal cathode catalyst material comprises:
(1) Dissolving zinc nitrate in a methanol solvent, adding an imidazole monomer after the zinc nitrate is completely dissolved, continuously stirring until the solution is milky, standing for emulsification, and finally centrifuging, washing and drying to obtain a zeolite imidazole ester metal organic framework material ZIF-8;
(2) Adding ferric salt, nitrogen-containing organic matters and zeolite imidazole metal organic framework material ZIF-8 into a ball milling tank according to a certain proportion, and performing ball milling to obtain a uniform powder mixture M/ZIF containing transition metal;
(3) Dispersing the M/ZIF mixture in an alcohol/water mixed solvent, fully stirring and standing, enabling iron ions, a nitrogen-containing ligand and ZIF-8 in the powder to coordinate with each other, removing the iron ions and monomers which are not coordinated through centrifugation and washing, and drying to obtain a uniformly dispersed monoatomic M-ZIF precursor;
(4) And finally, placing the M-ZIF precursor in a tube furnace, and performing two-step calcination pyrolysis to obtain the final monoatomic dispersion M-N-C catalyst material.
The invention also comprises the non-noble metal cathode catalyst material prepared by the method. The non-noble metal catalyst material is a nitrogen-doped carbon material uniformly distributed with transition metal monoatoms, wherein the transition metal is one or more of Fe, cu, co, ni and Mn; the content of transition metal in the non-noble metal cathode catalyst material is 1-10wt%.
The material provided by the invention has monoatomically dispersed M-N-C catalytic active sites and high active site density; the metal ions in the transition metal salt, the nitrogen-containing ligand and the metal organic framework polymer are coordinated through molecular self-assembly to obtain a uniformly dispersed monoatomic M-ZIF precursor; finally, the M-N-C catalyst material with single atom dispersion is prepared through two-step pyrolysis, and the catalyst material is applied to a fuel cell cathode and has excellent electrochemical performance.
The invention also comprises the application of the non-noble metal cathode catalyst material in preparing proton exchange membrane fuel cells (including oxyhydrogen fuel cells and hydrogen air fuel cells).
Basic principle: the transition metal salt, the nitrogen-containing complex and the imidazole ester metal organic framework material ZIF-8 which are uniformly mixed are coordinated with each other in a mixed solvent, and transition metal elements are effectively anchored in an imidazole framework structure in a single-atom form due to the steric hindrance effect of an imidazole framework, the static effect and the complex, and the transition metal-doped nitrogen-carbon catalyst material with single-atom distribution is prepared during subsequent two-step pyrolysis.
The beneficial effects are that: compared with the prior art, the invention has at least one of the following remarkable effects: 1) The single-atom dispersed transition metal doped nitrogen-carbon catalyst material is prepared by utilizing a molecular self-assembly strategy; 2) Preparing a monoatomic catalyst material with high active site density, high catalytic activity and high stability through two-step pyrolysis; 3) The preparation method is simple and controllable, has high consistency and is easy to realize mass production; 4) Applications exhibit ultra-high output power in fuel cells.
Drawings
Fig. 1: SEM image of ZIF-8 precursor material prepared in example 1 of the present invention.
Fig. 2: example 1 of the present invention produces an infrared test curve (FTIR) plot of ZIF-8, fe/ZIF materials.
Fig. 3: HAADF map of Fe/N/C catalyst material prepared according to inventive example 1.
Fig. 4: example 1 of the present invention prepares a polarization curve for Fe/N/C catalyst materials in hydrogen-oxygen fuel cells.
Fig. 5: example 1 of the present invention prepares a polarization curve for Fe/N/C catalyst materials in hydrogen-air fuel cells.
Fig. 6: SEM image of ZIF-8 precursor material prepared in example 2 of the present invention.
Fig. 7: comparative plots of Linear Sweep Voltammetry (LSV) curves for the preparation of Fe/N/C catalyst materials according to examples 1 and 2 of the present invention.
Fig. 8: comparative plot of Linear Sweep Voltammetry (LSV) curves for Fe/N/C catalyst materials prepared in inventive example 1 and comparative example 1.
Fig. 9: comparative plot of Linear Sweep Voltammetry (LSV) curves for Fe/N/C catalyst materials prepared in inventive example 1 and comparative example 2.
Fig. 10: comparative plot of Linear Sweep Voltammetry (LSV) curves for the preparation of Fe/N/C catalyst materials in inventive example 1 and comparative example 3.
Fig. 11: comparative plot of Linear Sweep Voltammetry (LSV) curves for the preparation of Fe/N/C catalyst materials in inventive example 2 and comparative example 4.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention. The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
Example 1
The embodiment provides a non-noble metal cathode catalyst material, and the preparation method thereof is as follows:
(1) 10g of Zn (NO 3)2·6H2 O is dissolved in 1L of methanol and fully stirred, after the complete and uniform dissolution, 11g of 2-methylimidazole is weighed and dissolved in the solution, and the solution is continuously fully stirred for 1h to obtain a milky white solution, and the solution is kept stand for 24h, and then centrifuged, washed and dried to prepare ZIF-8 (powder).
The process of this example gives an average of 3 g/batch of ZIF-8 powder.
(2) 50Mg of iron (II) acetate, 500mg of 1, 10-phenanthroline and 2000mg of ZIF-8 are weighed according to the proportion of 1:10:40, and are added into a ball milling tank, 100g of ball milling beads (the beads are 1mm,2mm and 3 mm-diameter zirconia mixed beads) are weighed, the ball milling rotating speed is set to be 240rpm, the ball milling time is 8 hours, and after the ball milling is finished, the powder is taken out to obtain a mixture Fe/ZIF of the iron-containing element, the nitrogen-containing complex and the imidazole metal organic framework.
(3) Dissolving the Fe/ZIF mixture in a mixed solvent of methanol/water (volume ratio is 5:1), fully stirring for 1h, standing for 12h, and centrifuging, washing and drying after the powder is completely coordinated and crystallized to obtain the Fe-ZIF.
(5) Weighing Fe-ZIF powder in a corundum crucible, placing the corundum crucible in a tube furnace, and performing secondary calcination in a nitrogen atmosphere, wherein the primary calcination temperature is 400 ℃, and calcining for 2 hours; the second calcination temperature is 1000 ℃, and calcination is carried out for 1h.
The non-noble metal cathode catalyst material prepared in this example was 0.9g.
FIG. 1 is an SEM image of a ZIF-8 precursor material prepared according to example 1.
FIG. 2 is an infrared test curve (FTIR) graph of the preparation of ZIF-8, fe/ZIF material of example 1, wherein the doped ZIF-8 has a significant right shift of N-H bonds, indicating the introduction of a large number of electron withdrawing groups on the framework. In the preparation method of the embodiment, only o-phenanthroline groups are adopted, so that the coordination form between the o-phenanthroline iron and the ZIF-8 is fully proved.
FIG. 3 is a HAADF diagram of the Fe/N/C catalyst material prepared in this example 1, and it can be seen from FIG. 3 that all Fe elements are distributed in the form of single atoms.
FIG. 4 is a graph showing the polarization of Fe/N/C catalyst material prepared in example 1 applied to hydrogen-oxygen fuel cells.
FIG. 5 is a graph showing the polarization of Fe/N/C catalyst material prepared in example 1 applied to a hydrogen-air fuel cell.
Example 2
This example provides a non-noble metal cathode catalyst material, the preparation method of which differs from example 1 only in that: the addition amount of "Zn (NO 3)2·6H2 O" and "2-methylimidazole" in the step (1) was amplified ten times by comparison, i.e., 100g of "Zn (NO 3)2·6H2 O" and 110g of "2-methylimidazole" were added.
6G of a non-noble metal cathode catalyst material was prepared in this example.
FIG. 6 is an SEM image of a ZIF-8 precursor material prepared according to example 2. It is obvious that the particle size of the ZIF-8 prepared by synchronously amplifying the concentration of the precursor is obviously increased.
FIG. 7 is a graph comparing Linear Sweep Voltammetry (LSV) curves for the preparation of Fe/N/C catalyst materials of examples 1 and 2 of the present invention. As can be deduced from fig. 7, the difference in oxygen reduction catalytic activity is small although the two catalysts are greatly different in particle size.
As can be seen, the ZIF-8 yield obtained in example 2 is increased in a comparable manner, and more importantly, the ZIF-8 particles obtained have a particle size several tens of times greater than that of example 1, but have very small differences in performance.
Comparative example 1
The only difference from example 1 is that: omitting the 1, 10-phenanthroline nitrogen coordination monomer in the step (2).
FIG. 8 is a graph comparing Linear Sweep Voltammetry (LSV) curves for the preparation of Fe/N/C catalyst materials of example 1 and comparative example 1 of the present invention. As can be seen from FIG. 8, the Fe/N/C catalyst material prepared in comparative example 1 without adding 1, 10-phenanthroline nitrogen-containing monomer has much lower oxygen reduction catalytic activity than that of example 1.
Comparative example 2
The only difference from example 1 is that: and (3) omitting the ball milling step in the step (2).
FIG. 9 is a graph comparing Linear Sweep Voltammetry (LSV) curves for the preparation of Fe/N/C catalyst materials of example 1 and comparative example 2 of the present invention. As can be deduced from fig. 9, the Fe/N/C catalyst material prepared without ball milling in comparative example 2 had lower oxygen reduction catalytic activity than in example 1 after ball milling.
Comparative example 3
The only difference from example 1 is that: and (5) calcining for 1 hour at the temperature of 1000 ℃ only once.
FIG. 10 is a graph comparing Linear Sweep Voltammetry (LSV) curves for the preparation of Fe/N/C catalyst materials of example 1 and comparative example 3 of the present invention. As can be deduced from FIG. 10, the Fe/N/C catalyst material obtained by the secondary calcination of example 1 has higher oxygen reduction catalytic activity than that of comparative example 3 by the primary calcination.
Comparative example 4
The only difference from example 2 is that: and (5) calcining for 1 hour at the temperature of 1000 ℃ only once.
FIG. 11 is a graph comparing Linear Sweep Voltammetry (LSV) curves for the preparation of Fe/N/C catalyst materials of example 2 and comparative example 4 of the present invention. As can be deduced from FIG. 11, the Fe/N/C catalyst material obtained by the secondary calcination of example 2 has higher oxygen reduction catalytic activity than that of comparative example 4 by the primary calcination.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (13)
1. A method of preparing a non-noble metal cathode catalyst material comprising:
Mixing transition metal salt, nitrogen-containing organic matters and zeolite imidazole ester metal organic framework material ZIF, and ball milling to obtain uniform powder mixture M/ZIF containing transition metal;
Dispersing a powder mixture M/ZIF containing transition metal in a solvent to coordinate the transition metal ions, the nitrogen-containing organic matters and the zeolite imidazole ester metal organic framework material ZIF; then removing transition metal ions and nitrogenous organic matters which are not coordinated; drying to obtain an M-ZIF precursor containing transition metal monoatoms which are uniformly distributed;
Calcining and pyrolyzing an M-ZIF precursor containing single atoms of transition metal in two steps to obtain a single-atom-distributed transition metal-doped nitrogen-carbon material, namely a non-noble metal cathode catalyst material;
In the two-step calcination pyrolysis, the temperature range of the first-step calcination pyrolysis is 200-600 ℃, and the time of the calcination pyrolysis is 1-10h; the temperature range of the second step of calcination pyrolysis is 900-1100 ℃, and the time of calcination pyrolysis is 1-10h.
2. The method for preparing a non-noble metal cathode catalyst material according to claim 1, wherein the zeolite imidazole metal organic framework material ZIF is selected from ZIF-8 and ZIF-67; and/or the number of the groups of groups,
The preparation method of the zeolite imidazole ester metal organic framework material ZIF comprises the following steps: and dissolving zinc salt in a methanol solvent, adding an imidazole monomer after the zinc salt is completely dissolved, continuously stirring until the solution is milky white, standing for emulsification, and finally centrifuging, washing and drying to obtain the zeolite imidazole ester metal organic framework material ZIF.
3. The method for preparing a non-noble metal cathode catalyst material according to claim 1 or 2, wherein the mass ratio of the ball materials during ball milling is 100-10:1; and/or the number of the groups of groups,
The rotation speed of the ball milling is 200-1000 rpm, and the ball milling time is 1-24 h.
4. The preparation method of the non-noble metal cathode catalyst material according to claim 1 or 2, wherein the mass ratio of the transition metal salt, the nitrogen-containing organic matter and the zeolite imidazole ester metal organic framework material ZIF is 1 (5-20): 20-100.
5. The method for preparing a non-noble metal cathode catalyst material according to claim 1 or 2, wherein the mass ratio of the transition metal salt, the nitrogen-containing organic matter and the zeolitic imidazolate metal organic framework material ZIF is 1:10:40.
6. The production method of a non-noble metal cathode catalyst material according to claim 1 or 2, wherein the transition metal is one or more of Fe, cu, co, ni and Mn; preferably, the transition metal salt is selected from one or more of chloride, nitrate, sulfate, acetate, citrate and acetylacetone compounds of the transition metal; and/or the number of the groups of groups,
The nitrogenous organic matters are one or more of phenanthroline, acetamide, ethylamine, pyrrole, aniline, ethylenediamine, dopamine, dicyandiamide, urea, butyronitrile and melamine.
7. The method for producing a non-noble metal cathode catalyst material according to claim 1 or 2, wherein the transition metal salt is one or more of chloride, nitrate, sulfate, acetate, citrate, acetylacetonate of Fe; the nitrogenous organic matter is phenanthroline.
8. The method for producing a non-noble metal cathode catalyst material according to claim 1 or 2, wherein the first-step calcination pyrolysis is performed at 400 ℃ for 2 hours; the pyrolysis temperature of the second calcination is 1000 ℃ and the time is 1h.
9. The method for producing a non-noble metal cathode catalyst material according to claim 1 or 2, comprising:
(1) Dissolving zinc nitrate in a methanol solvent, adding an imidazole monomer after the zinc nitrate is completely dissolved, continuously stirring until the solution is milky, standing for emulsification, and finally centrifuging, washing and drying to obtain a zeolite imidazole ester metal organic framework material ZIF-8;
(2) Adding ferric salt, nitrogen-containing organic matters and zeolite imidazole metal organic framework material ZIF-8 into a ball milling tank according to a certain proportion, and performing ball milling to obtain a uniform powder mixture M/ZIF containing transition metal;
(3) Dispersing the M/ZIF mixture in an alcohol/water mixed solvent, fully stirring and standing, enabling iron ions, a nitrogen-containing ligand and ZIF-8 in the powder to coordinate with each other, removing the iron ions and monomers which are not coordinated through centrifugation and washing, and drying to obtain a uniformly dispersed monoatomic M-ZIF precursor;
(4) And finally, placing the M-ZIF precursor in a tube furnace, and performing two-step calcination pyrolysis to obtain the final monoatomic dispersion M-N-C catalyst material.
10. A non-noble metal cathode catalyst material prepared by the method of any one of claims 1-8.
11. The non-noble metal cathode catalyst material of claim 10, wherein the transition metal in the non-noble metal cathode catalyst material is one or more of Fe, cu, co, ni and Mn; the content of the transition metal is 1-10wt%.
12. Use of the non-noble metal cathode catalyst material of claim 10 or 11 in the preparation of proton exchange membrane fuel cells.
13. The use of claim 12, wherein the proton exchange membrane fuel cell comprises an oxyhydrogen fuel cell, a hydrogen air fuel cell.
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