CN114243037A - Metal nitrogen-carbon loaded low-platinum ordered alloy composite catalyst and preparation method thereof - Google Patents
Metal nitrogen-carbon loaded low-platinum ordered alloy composite catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 36
- 239000002184 metal Substances 0.000 title claims abstract description 34
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 32
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 24
- 239000000956 alloy Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 229910001260 Pt alloy Inorganic materials 0.000 claims abstract description 9
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- 239000011572 manganese Substances 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 26
- 238000000227 grinding Methods 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- 229910052723 transition metal Inorganic materials 0.000 claims description 15
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical group [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 13
- -1 transition metal salt Chemical class 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 9
- 150000004032 porphyrins Chemical class 0.000 claims description 8
- 229910002837 PtCo Inorganic materials 0.000 claims description 7
- 229910002836 PtFe Inorganic materials 0.000 claims description 7
- 229910002844 PtNi Inorganic materials 0.000 claims description 7
- 150000003057 platinum Chemical class 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910019041 PtMn Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 150000002678 macrocyclic compounds Chemical class 0.000 claims description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
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- 239000004202 carbamide Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 3
- 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 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 150000003983 crown ethers Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 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 1
- 229910052786 argon Inorganic materials 0.000 claims 1
- 150000004696 coordination complex Chemical class 0.000 claims 1
- 239000012046 mixed solvent Substances 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001301 oxygen Substances 0.000 abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 abstract description 11
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000446 fuel Substances 0.000 abstract description 4
- 230000010757 Reduction Activity Effects 0.000 abstract description 3
- CMHKGULXIWIGBU-UHFFFAOYSA-N [Fe].[Pt] Chemical compound [Fe].[Pt] CMHKGULXIWIGBU-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000013112 stability test Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 31
- 238000001816 cooling Methods 0.000 description 20
- 238000009210 therapy by ultrasound Methods 0.000 description 20
- 239000000843 powder Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- 238000005554 pickling Methods 0.000 description 10
- 238000002390 rotary evaporation Methods 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229960001701 chloroform Drugs 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 230000010287 polarization Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 3
- 238000007630 basic procedure Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 2
- AQBLLJNPHDIAPN-LNTINUHCSA-K iron(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Fe+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AQBLLJNPHDIAPN-LNTINUHCSA-K 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- SEQUALWBCFCDGP-UHFFFAOYSA-N [C].[N].[Fe] Chemical compound [C].[N].[Fe] SEQUALWBCFCDGP-UHFFFAOYSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000012512 characterization method Methods 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
- FCEOGYWNOSBEPV-FDGPNNRMSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FCEOGYWNOSBEPV-FDGPNNRMSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- ZQZQURFYFJBOCE-FDGPNNRMSA-L manganese(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Mn+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O ZQZQURFYFJBOCE-FDGPNNRMSA-L 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
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Images
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
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group 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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- 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
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
Abstract
The invention discloses a metal nitrogen carbon loaded low-platinum ordered alloy composite catalyst and a preparation method thereof, wherein the composite catalyst comprises metal nitrogen carbon and platinum alloy loaded on the metal nitrogen carbon, and metal elements in the metal nitrogen carbon are one or more elements of iron, cobalt, nickel, copper and manganese; the platinum alloy contains 2.0-8.6% of platinum and the balance of one or more elements of iron, cobalt, nickel, copper and manganese. The invention successfully prepares the low platinum-carrying capacity platinum-based ordered alloy loaded on metal nitrogen carbon by regulating and controlling parameters such as heat treatment temperature, nitrogen source, carbon carrier and the like. The metal nitrogen carbon-loaded platinum-iron ordered alloy composite catalyst prepared by the method has excellent oxygen reduction activity and stability, the mass activity under the acidic condition of 0.9V is 3 times that of commercial platinum carbon, the mass activity under the alkaline condition reaches 6.9 times that of the commercial platinum carbon, and the performance after 30000-circle stability test is kept to be 82.55% of the initial value. The composite catalyst can be used for preparing a low platinum membrane electrode of a fuel cell.
Description
Technical Field
The invention relates to the field of proton exchange membrane fuel cell catalysts, in particular to a metal nitrogen-carbon-loaded low-platinum ordered alloy composite catalyst and a preparation method thereof.
Background
The fuel cell is an electrochemical power generation device without Carnot cycle, and has the advantages of cleanness, high efficiency, high energy conversion rate and the like. However, the slow kinetics of the cathodic oxygen reduction reaction during energy conversion severely hampers the overall efficiency of the fuel cell. In the current research, the platinum-based catalyst is the only metal catalyst that has good performance and durability in an acidic medium, but the expensive price and low reserves of platinum limit the large-scale commercial application of the platinum.
In order to reduce the amount of noble metal platinum and improve the utilization rate of platinum, the solution strategy generally has the following two directions. One is to synthesize the catalyst by alloying platinum and transition metal, and the doping of the transition metal can regulate and control the electronic structure of platinum, weaken the adsorption of intermediate products and improve the oxygen reduction activity and stability. However, the alloy is generally synthesized under high-temperature annealing, and the particles are easy to aggregate and grow, which brings about reduction of the electrochemical surface area. Another strategy is to develop a platinum-free metal catalyst, and the most mature research at present is a metal nitrogen carbon structure, which has the advantages of low cost and strong structure regulation, but the most fatal problems are poor ORR activity and poor durability. The synthesis of the composite catalyst usually requires the synthesis of the carrier first and then the loading of Pt, and the steps are complex.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a metal nitrogen-carbon loaded low-platinum ordered alloy composite catalyst with high catalytic activity and good stability; the invention also aims to provide a preparation method of the metal nitrogen-carbon-loaded low-platinum ordered alloy composite catalyst, which does not need step-by-step synthesis and has shortened reaction time.
The technical scheme is as follows: the metal nitrogen carbon loaded low-platinum ordered alloy composite catalyst comprises metal nitrogen carbon and a platinum alloy loaded on the metal nitrogen carbon, wherein metal elements in the metal nitrogen carbon are one or more elements of iron, cobalt, nickel, copper and manganese; the platinum alloy contains 2.0-8.6% of platinum and the balance of one or more elements of iron, cobalt, nickel, copper and manganese.
Further, the composite catalyst is PtFe @ FeNC, PtCo @ CoNC, PtNi @ NiNC, PtCu @ CuNC or PtMn @ MnNC.
On the other hand, the preparation method of the metal nitrogen-carbon loaded low-platinum ordered alloy composite catalyst comprises the following steps:
(1) uniformly dispersing platinum salt, transition metal salt and nitrogen source in a solvent, and then adding carbon black and further uniformly mixing to obtain a mixed solution;
(2) removing the solvent in the mixed solution, drying and grinding the mixed solution, and carrying out annealing heat treatment to obtain a sample;
(3) and (3) washing the sample in acid, drying, and carrying out secondary annealing heat treatment to obtain the product.
Further, in the step (1), the platinum salt is platinum acetylacetonate or chloroplatinic acid; the carbon black is XC-72, BP-2000, EC-300 or EC-600.
Further, in the step (1), the cation of the transition metal salt is one or more of iron, cobalt and nickel, and the anion of the transition metal salt is one or more of nitrate, acetate and acetylacetone salt.
Further, in the step (1), the nitrogen source is a macrocyclic compound or an organic compound which contains nitrogen and simultaneously performs coordination complexation with the transition metal cation.
Still further, the macrocyclic compound is a phthalocyanine, porphyrin or crown ether; the organic compound is urea, melamine ZIF-67 or ZIF-8.
Further, in the step (1), the molar ratio of the platinum salt to the transition metal salt is 1: 10-4: 10; the molar ratio of the transition metal salt to the nitrogen source is 1:2 to 1: 10.
Further, in the step (1), the solvent is one or more of chloroform, absolute ethyl alcohol and water.
Further, in the step (2) and/or the step (3), the annealing temperature is 800-.
Further, in the step (2), the drying method is natural drying, heating drying or vacuum drying.
According to the invention, the platinum alloy and the metal nitrogen carbon are combined to prepare the metal nitrogen carbon loaded low-platinum ordered alloy composite catalyst, and in the structure, the metal nitrogen carbon provides additional active sites in the catalyst, so that the platinum load in the cathode oxygen reduction reaction is reduced; the nitrogen-doped sites in the metal nitrocarbon can strengthen the metal-carrier interaction and stabilize the nanoparticles, and meanwhile, the synergistic effect existing between the platinum and the metal nitrocarbon sites with dispersed atoms can further improve the catalytic activity and stability.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: (1) the catalytic activity is obviously improved, and the synthesis of the metal nitrogen-carbon-supported ordered alloy composite catalyst by a one-step calcination method is directly realized by introducing a nitrogen source into a precursor for preparing the ordered alloy without adopting the traditional two-step method of firstly synthesizing carrier metal nitrogen-carbon and then loading platinum thereon to prepare the composite catalyst;
(2) the stability is obviously improved, the ordered platinum alloy is successfully prepared by using platinum salt and transition metal salt and reasonably regulating and controlling the reactant proportion under the condition of low metal addition amount, and the ordered structure is favorable for improving the catalytic activity and the stability of the catalyst;
(3) the composite catalyst shows excellent oxygen reduction activity and stability, the mass activity under an acidic condition of 0.9V (relative to a standard hydrogen electrode) is 3 times that of commercial platinum carbon, the mass activity under an alkaline condition reaches 6.9 times that of the commercial platinum carbon, and the performance after 30000 circles of stability test is kept to be 82.55% of the initial value.
(4) The process flow is compact and efficient, the graphitization degree of the metal nitrogen carbon and the ordering degree of the platinum alloy are promoted by two times of heat treatment, and oxides which are unfavorable to the catalyst and are generated in the heat treatment process are removed by acid washing;
(5) the method has the advantages of simple operation, high repeatability, easy production amplification synthesis, and no use of surfactant in the whole preparation process.
Drawings
FIG. 1 is a schematic diagram of the synthesis of a catalyst obtained in example 1 of the present invention;
FIG. 2 is a graph comparing the oxygen reduction polarization curve test results of the catalysts obtained in examples 1 to 5 of the present invention;
FIG. 3 is a TEM image and interplanar spacings of the catalyst obtained in example 1 of the present invention;
FIG. 4 is a comparative XRD pattern of the catalysts obtained in example 1 and comparative examples 1 to 3 of the present invention;
FIG. 5 is a graph comparing the results of oxygen reduction polarization curve tests of catalysts obtained in example 1 of the present invention, comparative examples 1-3, and JM 20% commercial platinum carbon;
FIG. 6 is a graph comparing the oxygen reduction polarization curve test results before and after 30000 cycles of accelerated aging for the catalyst obtained in example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
Example 1
The PtFe @ FeNC composite catalyst comprises FeNC and PtFe alloy loaded on the FeNC, wherein the content of platinum is 2.0 percent; as shown in fig. 1, the specific preparation steps are as follows:
(1) adding 4.4mg of platinum (II) acetylacetonate, 33.5mg of iron (III) acetylacetonate and 140mg of porphyrin into trichloromethane, carrying out ultrasonic treatment until the solution is uniformly dispersed, adding 75mg of EC-600 conductive carbon black, and carrying out ultrasonic treatment to obtain a uniformly mixed solution;
(2) carrying out rotary evaporation treatment on the solution, removing the solvent, and naturally drying overnight; grinding the dried sample into powder, heating to 900 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, preserving the heat for 2 hours, and naturally cooling to room temperature;
(3) the annealed sample was set at 0.5M H2SO4Pickling in the solution, filtering, and naturally drying overnight; grinding the dried product into powder, and performing a second heat treatment with the condition parameters of the first heat treatmentAnd (4) completely consistent, and naturally cooling to room temperature to obtain the PtFe @ FeNC composite catalyst.
Example 2
The PtCo @ CoNC composite catalyst comprises CoNC and PtCo alloy loaded on the CoNC, wherein the content of platinum is 5.8 percent; the preparation method comprises the following specific steps:
(1) adding 10mg of platinum (II) acetylacetonate, 51.4mg of cobalt (II) acetylacetonate and 140mg of porphyrin into trichloromethane, carrying out ultrasonic treatment until the solution is uniformly dispersed, adding 75mg of EC-600 conductive carbon black, and carrying out ultrasonic treatment to obtain a uniformly mixed solution;
(2) carrying out rotary evaporation treatment on the solution, removing the solvent, and naturally drying overnight; grinding the dried sample into powder, heating to 900 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, preserving the heat for 2 hours, and naturally cooling to room temperature;
(3) the annealed sample was set at 0.5M H2SO4Pickling in the solution, filtering, and naturally drying overnight; and grinding the dried product into powder, carrying out secondary heat treatment, and naturally cooling to room temperature to obtain the PtCo @ CoNC composite catalyst, wherein the condition parameters are completely consistent with those of the primary heat treatment.
Example 3
The PtNi @ NiNC composite catalyst comprises NiNC and PtNi alloy loaded on the NiNC, wherein the content of platinum is 8.6 percent; the preparation method comprises the following specific steps:
(1) adding 17.6mg of platinum (II) acetylacetonate, 51.3mg of nickel (II) acetylacetonate and 140mg of porphyrin into trichloromethane, carrying out ultrasonic treatment until the solution is uniformly dispersed, adding 75mg of EC-600 conductive carbon black, and carrying out ultrasonic treatment to obtain a uniformly mixed solution;
(2) carrying out rotary evaporation treatment on the solution, removing the solvent, and naturally drying overnight; grinding the dried sample into powder, heating to 900 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, preserving the heat for 2 hours, and naturally cooling to room temperature;
(3) the annealed sample was set at 0.5M H2SO4Pickling in the solution, filtering, and naturally drying overnight; grinding the dried product into powderAnd (3) performing second heat treatment, wherein the condition parameters are completely consistent with those of the first heat treatment, and naturally cooling to room temperature to obtain the PtNi @ NiNC composite catalyst.
Example 4
The preparation method of the PtCu @ CuNC composite catalyst comprises the following steps:
(1) adding 4.4mg of platinum (II) acetylacetonate, 52.3mg of copper (II) acetylacetonate and 140mg of porphyrin into trichloromethane, carrying out ultrasonic treatment until the solution is uniformly dispersed, adding 75mg of EC-600 conductive carbon black, and carrying out ultrasonic treatment to obtain a uniformly mixed solution;
(2) carrying out rotary evaporation treatment on the solution, removing the solvent, and naturally drying overnight; grinding the dried sample into powder, heating to 900 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, preserving the heat for 2 hours, and naturally cooling to room temperature;
(3) the annealed sample was set at 0.5M H2SO4Pickling in the solution, filtering, and naturally drying overnight; and grinding the dried product into powder, carrying out secondary heat treatment, and naturally cooling to room temperature to obtain the PtCu @ CuNC composite catalyst, wherein the condition parameters are completely consistent with those of the primary heat treatment.
Example 5
The preparation method of the PtMn @ MnNC composite catalyst comprises the following steps:
(1) adding 4.4mg of platinum (II) acetylacetonate, 50.6mg of manganese (II) acetylacetonate and 140mg of porphyrin into trichloromethane, carrying out ultrasonic treatment until the solution is uniformly dispersed, adding 75mg of EC-600 conductive carbon black, and carrying out ultrasonic treatment to obtain a uniformly mixed solution;
(2) carrying out rotary evaporation treatment on the solution, removing the solvent, and naturally drying overnight; grinding the dried sample into powder, heating to 900 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, preserving the heat for 2 hours, and naturally cooling to room temperature;
(3) the annealed sample was set at 0.5M H2SO4Pickling in the solution, filtering, and naturally drying overnight; grinding the dried product into powder, carrying out secondary heat treatment, and naturally cooling to room temperature to obtain the final productPtMn @ MnNC composite catalyst.
Example 6
The preparation method of the PtFe @ FeNC composite catalyst comprises the following steps:
(1) adding 4.4mg of platinum (II) acetylacetonate, 48.3mg of ferric nitrate (III) and 50.4mg of melamine into trichloromethane, carrying out ultrasonic treatment until the solution is uniformly dispersed, adding 75mg of EC-600 conductive carbon black, and carrying out ultrasonic treatment to obtain a uniformly mixed solution;
(2) carrying out rotary evaporation treatment on the solution, removing the solvent, and then carrying out vacuum drying overnight; grinding the dried sample into powder, heating to 900 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, preserving the heat for 4 hours, and naturally cooling to room temperature;
(3) the annealed sample was set at 0.5M H2SO4Pickling in the solution, filtering, and naturally drying overnight; and grinding the dried product into powder, carrying out secondary heat treatment, and naturally cooling to room temperature to obtain the PtFe @ FeNC composite catalyst, wherein the condition parameters are completely consistent with those of the primary heat treatment.
Example 7
The preparation method of the PtCo @ CoNC composite catalyst comprises the following steps:
(1) adding 4.4mg of platinum (II) acetylacetonate, 53.1mg of cobalt (II) acetate and 93.6mg of ZIF-8 into absolute ethyl alcohol, carrying out ultrasonic treatment until the solution is uniformly dispersed, adding 75mg of EC-600 conductive carbon black, and carrying out ultrasonic treatment to obtain a uniformly mixed solution;
(2) carrying out rotary evaporation treatment on the solution, removing the solvent, and naturally drying overnight; grinding the dried sample into powder, heating to 800 ℃ at the speed of 5 ℃/min in the nitrogen atmosphere, preserving the heat for 5 hours, and naturally cooling to room temperature;
(3) the annealed sample was set at 0.5M H2SO4Pickling in the solution, filtering, and naturally drying overnight; and grinding the dried product into powder, carrying out secondary heat treatment, and naturally cooling to room temperature to obtain the PtCo @ CoNC composite catalyst, wherein the condition parameters are completely consistent with those of the primary heat treatment.
Example 8
The preparation method of the PtNi @ NiNC composite catalyst comprises the following steps:
(1) adding 8.8mg of platinum (II) acetylacetonate, 18.6mg of nickel (II) nitrate and 411.6mg of phthalocyanine into absolute ethyl alcohol, carrying out ultrasonic treatment until the solution is uniformly dispersed, adding 75mg of EC-600 conductive carbon black, and carrying out ultrasonic treatment to obtain a uniformly mixed solution;
(2) carrying out rotary evaporation treatment on the solution, removing the solvent, and naturally drying overnight; grinding the dried sample into powder, heating to 800 ℃ at the speed of 5 ℃/min under the argon atmosphere, preserving the temperature for 6 hours, and naturally cooling to room temperature;
(3) the annealed sample was set at 0.5M H2SO4Pickling in the solution, filtering, and naturally drying overnight; and grinding the dried product into powder, carrying out secondary heat treatment, and naturally cooling to room temperature to obtain the PtNi @ NiNC composite catalyst, wherein the condition parameters are completely consistent with those of the primary heat treatment.
Example 9
The preparation method of the PtCu @ CuNC composite catalyst comprises the following steps:
(1) adding 13.2mg of platinum (II) acetylacetonate, 104.7mg of copper (II) acetylacetonate and 300.2mg of urea into a mixed solution of absolute ethyl alcohol and water, carrying out ultrasonic treatment until the solution is uniformly dispersed, adding 75mg of EC-600 conductive carbon black, and carrying out ultrasonic treatment to obtain a uniformly mixed solution;
(2) carrying out rotary evaporation treatment on the solution, removing the solvent, and naturally drying overnight; grinding the dried sample into powder, heating to 1000 ℃ at the speed of 5 ℃/min under the argon atmosphere, preserving heat for 1 hour, and naturally cooling to room temperature;
(3) the annealed sample was set at 0.5M H2SO4Pickling in the solution, filtering, and naturally drying overnight; and grinding the dried product into powder, carrying out secondary heat treatment, and naturally cooling to room temperature to obtain the PtCu @ CuNC composite catalyst, wherein the condition parameters are completely consistent with those of the primary heat treatment.
Example 10:
the preparation method of the PtMn @ MnNC composite catalyst comprises the following steps:
(1) adding 17.6mg of platinum (II) acetylacetonate, 69.2mg of manganese acetate and 2.23g of ZIF-67 into a mixed solution of absolute ethyl alcohol and water, carrying out ultrasonic treatment until the solution is uniformly dispersed, adding 75mg of EC-600 conductive carbon black, and carrying out ultrasonic treatment to obtain a uniformly mixed solution;
(2) carrying out rotary evaporation treatment on the solution, removing the solvent, and naturally drying overnight; grinding the dried sample into powder, heating to 1000 ℃ at the speed of 5 ℃/min under the argon atmosphere, preserving the temperature for 2 hours, and naturally cooling to room temperature;
(3) the annealed sample was set at 0.5M H2SO4Pickling in the solution, filtering, and naturally drying overnight; and grinding the dried product into powder, carrying out secondary heat treatment, and naturally cooling to room temperature to obtain the composite PtMn @ MnNC catalyst, wherein the condition parameters are completely consistent with those of the primary heat treatment.
Comparative example 1:
the basic procedure was the same as in example 1, except that no porphyrin was added in this comparative example, and finally a platinum-iron ordered alloy catalyst supported on conductive carbon black was obtained.
Comparative example 2:
the basic procedure was the same as in example 1 except that platinum (II) acetylacetonate was not added to the comparative example, to finally obtain an iron-nitrogen-carbon catalyst.
Comparative example 2:
the basic procedure is the same as in example 1, except that in this comparative example, no iron (III) acetylacetonate is added, and a platinum/platinum-nitrogen-carbon catalyst is finally obtained.
The electrochemical properties of the catalysts obtained in examples 1 to 5 are respectively characterized, and the results of oxygen reduction polarization curve test of the five catalysts are shown in fig. 2, for example, it can be seen that the preparation method disclosed by the invention is suitable for all alloy elements such as platinum, iron, cobalt, nickel, copper, manganese and the like, and the composite catalysts prepared by the method all show excellent electrochemical properties.
The morphology of the catalyst obtained in example 1 is characterized, and a TEM image is shown in FIG. 3, so that the catalyst obtained in example 1 has uniform particle distribution, and HRTEM shows that the interplanar spacing is0.219 nm, corresponding to Pt3Fe (111) crystal plane.
The phase analysis was performed on the catalysts obtained in example 1 and comparative examples 1 to 3, and the XRD results of the four catalysts are shown in FIG. 4, which shows that the diffraction peak and Pt of the catalyst obtained in example 13The PDF cards of Fe correspond one to one, and a small and sharp superlattice diffraction peak appears in an XRD spectrogram at about 33 degrees, and the formation of the ordered alloy is confirmed by the appearance of the peak.
Electrochemical performance characterization is performed on example 1, comparative examples 1 to 3 and JM 20% commercial platinum-carbon respectively, and the results of oxygen reduction polarization curve test of the five are shown in FIG. 5, so that the performance of the iron-nitrogen-carbon-supported platinum-iron ordered alloy composite catalyst prepared in example 1 is obviously superior to that of the other four.
The aging resistance of the product prepared in example 1 is characterized, and the test results of the oxygen reduction polarization curves before and after 30000-cycle accelerated aging are shown in fig. 6, which shows that the catalyst prepared in example 1 has very little performance loss after 30000-cycle accelerated aging, and the mass activity only attenuates by 18.45%, thus indicating the excellent stability.
Claims (10)
1. The metal nitrogen carbon loaded low-platinum ordered alloy composite catalyst is characterized by comprising metal nitrogen carbon and platinum alloy loaded on the metal nitrogen carbon, wherein the metal element in the metal nitrogen carbon is one or more of iron, cobalt, nickel, copper and manganese; the platinum alloy contains 2.0-8.6% of platinum and the balance of one or more elements of iron, cobalt, nickel, copper and manganese.
2. The metal-nitrogen-carbon supported low-platinum ordered alloy composite catalyst according to claim 1, wherein the composite catalyst is PtFe @ FeNC, PtCo @ CoNC, PtNi @ NiNC, PtCu @ CuNC or PtMn @ MnNC.
3. A method for preparing the metal nitrogen-carbon supported low platinum ordered alloy composite catalyst according to any one of claims 1 to 2, which is characterized by comprising the following steps of:
(1) uniformly dispersing platinum salt, transition metal salt and nitrogen source in a solvent, and then adding carbon black and further uniformly mixing to obtain a mixed solution;
(2) removing the solvent in the mixed solution, drying and grinding the mixed solution, and carrying out annealing heat treatment to obtain a sample;
(3) and (3) washing the sample in acid, drying, and carrying out secondary annealing heat treatment to obtain the product.
4. The method according to claim 3, wherein in the step (1), the platinum salt is platinum acetylacetonate or chloroplatinic acid
5. The method according to claim 3, wherein in the step (1), the cation of the transition metal salt is one or more of iron, cobalt and nickel, and the anion of the transition metal salt is one or more of nitrate, acetate and acetylacetonate.
6. The method according to claim 3, wherein in the step (1), the nitrogen source is a macrocyclic compound or an organic compound containing nitrogen and having a coordination complex with the transition metal cation.
7. The method of claim 6, wherein the macrocyclic compound is a phthalocyanine, porphyrin or crown ether; the organic compound is urea, melamine ZIF-67 or ZIF-8.
8. The method according to claim 3, wherein in the step (1), the molar ratio of the platinum salt to the transition metal salt is 1:10 to 4: 10; the molar ratio of the transition metal salt to the nitrogen source is 1:2 to 1: 10.
9. The method according to claim 3, wherein in the step (1), the solvent is a mixed solvent of one or more of chloroform, absolute ethanol and water.
10. The method according to claim 3, wherein in step (2) and/or step (3), the annealing temperature is 800-1000 ℃, the annealing atmosphere is nitrogen or argon, and the annealing time is 1-6 h.
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