CN117766789A - Rare earth gadolinium doped high-stability platinum-based catalyst and preparation method and application thereof - Google Patents
Rare earth gadolinium doped high-stability platinum-based catalyst and preparation method and application thereof Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 83
- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 229910052688 Gadolinium Inorganic materials 0.000 title claims abstract description 49
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 49
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 21
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 14
- 238000011068 loading method Methods 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 12
- 239000000446 fuel Substances 0.000 claims description 11
- 239000002082 metal nanoparticle Substances 0.000 claims description 11
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000012018 catalyst precursor Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 150000000921 Gadolinium Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- PNYPSKHTTCTAMD-UHFFFAOYSA-K trichlorogadolinium;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Gd+3] PNYPSKHTTCTAMD-UHFFFAOYSA-K 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 238000010306 acid treatment Methods 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- XWFVFZQEDMDSET-UHFFFAOYSA-N gadolinium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XWFVFZQEDMDSET-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 13
- 239000000956 alloy Substances 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 6
- 239000012621 metal-organic framework Substances 0.000 abstract description 6
- 238000004873 anchoring Methods 0.000 abstract description 4
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 238000001212 derivatisation Methods 0.000 abstract description 3
- 230000000670 limiting effect Effects 0.000 abstract description 3
- 230000006911 nucleation Effects 0.000 abstract description 3
- 238000010899 nucleation Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 10
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- 239000012528 membrane Substances 0.000 description 6
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- 229910001260 Pt alloy Inorganic materials 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- 229910002837 PtCo Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241001559589 Cullen Species 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- -1 Pt 3 Co Chemical class 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- 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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Abstract
The invention discloses a rare earth gadolinium doped high-stability platinum-based catalyst, a preparation method and application thereof, wherein atomic-scale dispersion of rare earth gadolinium on a porous carbon substrate is realized through a metal-organic framework (MOF) derivatization strategy, rich anchoring sites are provided for nucleation growth of platinum-based alloy, and strong coupling between rare earth and platinum is ensured. Rare earth gadolinium is diffused into the lattices of platinum-based alloy particles by a high-temperature heat treatment method, meanwhile, agglomeration of particles under a high-temperature condition is inhibited by utilizing the limiting effect of porous carbon, the size of the formed platinum-based alloy particles is smaller, and the higher noble metal utilization rate is ensured. The preparation method is simple, low in cost and good in reproducibility, and compared with the existing commercial catalyst, the platinum-based alloy catalyst prepared based on the method is lower in noble metal consumption, higher in catalytic activity and better in stability.
Description
Technical Field
The invention belongs to the technical field of cathode catalysts, and particularly relates to a rare earth gadolinium doped high-stability platinum-based catalyst, and a preparation method and application thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are key technologies for achieving the aims of hydrogen-electricity conversion and power assistance of double carbon, have high energy density, high conversion efficiency and environmental friendliness, and are widely focused by researchers at home and abroad. The slow kinetics of the cathodic Oxygen Reduction Reaction (ORR) of fuel cells requires the catalysis of large amounts of noble metal platinum, which severely hampers the large-scale application of fuel cells due to the cost problems associated with the limited reserves of noble metal platinum resources. Therefore, the development of a low-platinum cathode catalyst with high activity and high stability is a hot spot of the current international energy chemistry front focusing.
The prior art can effectively improve the activity and stability of the platinum-based catalyst through morphology control, alloying, ordering and other modes, for example, a Huang team designs an ultra-fine PtCo nano catalyst protected by a graphene nano pocket, and under the extremely challenging ultra-low platinum loading condition, the mass normalization rated power of a membrane electrode of PtCo@Gnp can reach 13.2W mgPGM -1 And durability to international advanced levels (Yang, c.l.; wang, l.n.; yin, p.; liu, j.; chen, m.x.; yan, q.q.; wang, z.s.; xu, s.l.; chu, s.q.; cui, c.; ju, h.; zhu, j.; lin, y.; shoi, j.; liang, h.w.; sulfur-anchoring synthesis of platinum intermetallic nanoparticle catalysts for fuel cells.science2021,374 (6566), 459-464). Liang Haiwei A sulfur anchoring method based on platinum-based small-size intermetallic compounds, which uses strong interactions between platinum and sulfur atoms doped in a carbon matrix to inhibit sintering of particles up to 1000 ℃ and realize46 ordered intermetallic compounds with the particle size smaller than 5nm are formed at high temperature, and the prepared catalyst has excellent activity and stability; wu Gang a preparation method of a high-stability and high-activity platinum-based catalyst is developed, and the preparation method realizes the characteristics that proton exchange membrane fuel cells suitable for heavy vehicles (HDV) are required to have high power density and long service life (Zeng, Y.; liang, J.; li, C.; qiao, Z.; li, B.; hwang, S.; kariuki, N.N.; chang, C.W.; wang, M.; lyons, M.; lee, S.; feng, Z.; wang, G.; xie, J.; cullen, D.A.; myers, D.J.; wu, G.; regulating Catalytic Properties and Thermal Stability of Pt and PtCo Intermetallic Fuel-Cell Catalysts via Strong Coupling Effects between Single-al SiSing-Ribon and Carbonal (32-of the American Chemical Society, 32-43); although the activity of the catalyst is significantly improved after modification, such studies have focused on late transition metals such as Pt 3 Co，Pt 3 Ni，Pt 3 Fe, etc., while such materials exhibit excellent activity and stability in short-term accelerated degradation experiments, dissolution of the second element in long-term testing can lead to rapid degradation of the catalyst, as well as serious damage to the membrane electrode system as a whole.
In contrast, platinum and pre-transition metal alloys, especially rare earth elements, have exceptionally negative alloy energies on the basis of their superior oxygen species adsorption energies, both theoretical and experimental studies have shown that they have higher activity and stability (Escudero Escribano, m.; maldrida, p.; hansen Martin, h.; vej Hansen Ulrik, g.; vel zquez Palenzuela, a.; tripkovic, v.;j.; rossmeis, j.; stephens Ifan, e.l.; chorkandorff, I., tuning the activity of Pt alloy electrocatalysts by means of the lanthanide connection. Science2016,352 (6281), 73-76). However, since the standard reduction potentials of platinum and rare earth metals are very different, and rare earth metalsThe low reduction potential is far beyond the stable range of water and conventional wet chemical techniques are no longer suitable for synthesizing rare earth-based platinum alloy catalysts in nanoparticle form. Therefore, how to overcome the technical defects of low catalytic activity and poor catalytic stability caused by dissolution of platinum and second transition metal, particle agglomeration and the like of the proton exchange membrane fuel cell cathode catalyst in the prior art, realize stable doping of rare earth metal, and prepare a catalyst with high activity and high stability is a problem to be solved in the prior art.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
The present invention has been made in view of the above and/or problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a rare earth gadolinium doped high-stability platinum-based catalyst.
In order to solve the technical problems, the invention provides the following technical scheme: comprises a carbon carrier rich in atomic dispersion gadolinium, and a first metal nanoparticle and a second metal nanoparticle loaded on the surface of the carbon carrier;
the first metal nano particles are platinum, the second metal nano particles comprise one or more of iron, cobalt and nickel, the total loading amount of the metal nano particles is 5-50wt%, and the average particle size is less than 4.50nm.
Still another object of the present invention is to provide a method for preparing a rare earth gadolinium doped high stability platinum-based catalyst, comprising,
dissolving metal gadolinium salt and 1,3, 5-benzene tricarboxylic acid in a mixed solvent of water and N, N-dimethylformamide, heating and stirring, centrifugally separating, washing and drying to obtain a white solid, wherein the molar ratio of the metal gadolinium salt to the 1,3, 5-benzene tricarboxylic acid is 3:1-1:1;
performing heat treatment on the white solid in an inert gas atmosphere, and cooling to room temperature to obtain a carbon carrier rich in atomic-level dispersed gadolinium sites;
dispersing a carbon carrier in ultrapure water, adding a metal salt solution, stirring overnight, and performing rotary steaming treatment to obtain a catalyst precursor, wherein the mass of metal in the metal salt is 5-50wt% compared with the addition amount of the carbon carrier;
and carrying out heat treatment on the catalyst precursor in argon-hydrogen mixed gas, cooling, and then sequentially carrying out acid washing, suction filtration and drying to obtain the rare earth gadolinium doped high-stability platinum-based catalyst.
As a preferable scheme of the preparation method of the rare earth gadolinium doped high-stability platinum-based catalyst, the preparation method comprises the following steps: the metal gadolinium salt comprises one of gadolinium chloride hexahydrate and gadolinium nitrate hexahydrate.
As a preferable scheme of the preparation method of the rare earth gadolinium doped high-stability platinum-based catalyst, the preparation method comprises the following steps: the metal salt solution comprises a first metal salt solution and a second metal salt solution, wherein the first metal salt solution is a chloroplatinic acid aqueous solution, and the second metal salt solution comprises one or more of ferric chloride, cobalt chloride and nickel chloride aqueous solution.
As a preferable scheme of the preparation method of the rare earth gadolinium doped high-stability platinum-based catalyst, the preparation method comprises the following steps: the heating temperature of the heating and stirring is 50-100 ℃ and the heating time is 3-6 h.
As a preferable scheme of the preparation method of the rare earth gadolinium doped high-stability platinum-based catalyst, the preparation method comprises the following steps: the heat treatment is carried out in an inert gas atmosphere, wherein the inert gas comprises argon or nitrogen, the heating rate of the heat treatment is 1-10 ℃/min, the temperature is 800-1000 ℃, and the time is 0.5-3 h.
As a preferable scheme of the preparation method of the rare earth gadolinium doped high-stability platinum-based catalyst, the preparation method comprises the following steps: the catalyst precursor is subjected to heat treatment in an argon-hydrogen mixed gas, wherein the volume content of hydrogen in the argon-hydrogen mixed gas is 5-10 vol%.
As a preferable scheme of the preparation method of the rare earth gadolinium doped high-stability platinum-based catalyst, the preparation method comprises the following steps: the heating rate of the heat treatment is 0.5-10 ℃/min, the temperature is 600-1100 ℃ and the time is 1-4 h.
As a preferable scheme of the preparation method of the rare earth gadolinium doped high-stability platinum-based catalyst, the preparation method comprises the following steps: the acid treatment solution for acid washing is perchloric acid or dilute hydrochloric acid solution with the concentration of 0.1-1 mol/L.
It is a further object of the present invention to provide the use of rare earth gadolinium doped high stability platinum based catalysts as fuel cell cathode materials.
The invention has the beneficial effects that:
the invention realizes atomic-scale dispersion of rare earth gadolinium on a porous carbon substrate through a metal-organic framework (MOF) derivatization strategy, provides rich anchoring sites for nucleation growth of platinum-based alloy, ensures strong coupling between rare earth and platinum, effectively inhibits agglomeration of particles under high temperature condition, and ensures higher noble metal utilization rate due to smaller size of the formed platinum-based alloy particles. Compared with the existing commercial catalyst, the prepared rare earth gadolinium doped high-stability platinum-based fuel cell cathode catalyst has higher catalytic activity and better stability, and effectively solves the technical problems.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a graph showing the transmission electron microscope of the catalyst prepared in example 1 of the present invention.
FIG. 2 is a graph showing the statistical analysis of particle diameters of the catalyst-supported nanoparticles produced in example 1 of the present invention.
FIG. 3 is an elemental analysis chart of the catalyst-supported nanoparticle prepared in example 1 of the present invention.
FIG. 4 is an X-ray diffraction pattern of the catalyst prepared in example 1 of the present invention.
FIG. 5 is a graph showing the results of an accelerated aging test of the catalyst prepared in example 1 of the present invention.
Fig. 6 is a graph showing the peak power density test results of the catalyst of example 1 of the present invention assembled as a single cell as a cathode.
Fig. 7 is a graph showing the results of stability test of the catalyst of example 1 of the present invention assembled as a single cell as a cathode.
Fig. 8 is a graph showing the results of performance test of catalysts prepared by different heat treatment temperatures as cathodes assembled into single cells according to example 2 of the present invention.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The raw materials used in the invention are all common commercially available analytical pure in the field without special description.
Example 1
The embodiment provides a preparation method of a rare earth gadolinium doped high-stability platinum-based catalyst, which comprises the following steps:
1) 743.4mg of gadolinium chloride hexahydrate and 428.85mg of 1,3, 5-benzene tricarboxylic acid are weighed into a 250mL round bottom flask, 50mL of N, N dimethylformamide and 50mL of ultrapure water are added, the mixture is stirred until the mixture is clear, the mixture is stirred for 3 hours at 90 ℃, the mixture is centrifugally separated, the mixture is washed three times by a mixed solvent of ethanol and water, and then the mixture is dried in a drying box at 55 ℃ to obtain white solid;
2) Placing the obtained white solid in a tubular furnace, and performing heat treatment on the white solid in an argon atmosphere at a heating rate of 5 ℃/min, wherein the heat treatment temperature is 900 ℃ and the time is 1h, and naturally cooling the white solid to room temperature to obtain a carbon carrier rich in atomic-level dispersed gadolinium sites;
3) Dispersing 100mg of a carbon carrier in 50mL of ultrapure water, adding 1.50mL of a chloroplatinic acid solution (7.4 mgPt/mL) and 0.82mL of a nickel chloride solution (1.37 mgNi/mL) to carry out ultrasonic treatment for 30 minutes, and then stirring for 12 hours at room temperature, and carrying out rotary evaporation treatment on the obtained suspension to obtain a catalyst precursor;
4) And (3) placing the obtained precursor in a tube furnace, performing heat treatment in a mixed gas of 5vol% of argon and hydrogen, wherein the heating rate is 5 ℃/min, the heat treatment temperature is 1000 ℃, the time is 3h, the temperature is reduced to 400 ℃ at the cooling rate of 10 ℃/min, naturally cooling to room temperature, then pickling, suction filtering and drying to obtain the rare earth gadolinium doped high-stability platinum-based catalyst with the metal nano loading capacity of 35%.
The high-stability platinum-based catalyst prepared in the embodiment is subjected to transmission electron microscope characterization, and the result is shown in fig. 1, so that gadolinium-doped platinum-nickel alloy nano particles in the obtained catalyst are uniformly loaded on the surface of a carrier, and no obvious agglomeration occurs after high-temperature heat treatment.
The particle size of the nanoparticle carried in the high-stability platinum-based catalyst prepared in this example was statistically analyzed, and the result is shown in fig. 2, which shows that the average particle size of the nanoparticle is 4.30nm, and the particle size is small and uniformly distributed, which is advantageous for exposing more catalytic active sites.
The element analysis is carried out on the nano particles loaded in the high-stability platinum-based catalyst prepared in the embodiment, and the result is shown in figure 3, wherein the particles simultaneously contain platinum, nickel and gadolinium elements, and the doping of rare earth gadolinium is proved.
The high-stability platinum-based catalyst prepared in the embodiment is subjected to X-ray diffraction characterization, and the result is shown in fig. 4, so that the diffraction peak of the obtained catalyst is matched with that of a platinum-nickel alloy, the successful synthesis of the alloy is shown, and the doping of gadolinium causes compressive strain to the crystal lattice, so that the successful doping of gadolinium is shown.
The high-stability platinum-based catalyst prepared in the embodiment is subjected to accelerated aging test in 0.1mol/L perchloric acid solution, and the result is shown in fig. 5, the performance of the catalyst is not obviously degraded after the catalyst is subjected to seventy-thousand circles of accelerated aging test, and the catalyst shows excellent stability.
Application test:
the platinum-based catalyst prepared in the embodiment is used as a cathode assembled single cell for performance test, and is specific;
the prepared rare earth gadolinium doped platinum-based catalyst is taken as a cathode, and the loading capacity is 0.1mgPt cm -2 Commercial platinum carbon was the anode with a loading of 0.08mgPt cm -2 The membrane electrode was assembled and then tested for cell performance at 850e under conditions of 80 ℃, 200kPa back pressure, 100% humidification.
As a result, as shown in FIG. 6, it can be seen that the platinum loading of the fuel cell assembled with the rare earth gadolinium doped platinum-based fuel cell cathode catalyst as the cathode was 0.1mg cm -2 Under the condition, the peak power density can reach 2.05W cm -2 Has excellent catalytic activity.
The stability test was performed using the platinum-based catalyst prepared in this example as a cathode assembled cell, and the results are shown in fig. 7, and it can be seen that after performing the forty-thousand-cycle accelerated aging test in the potential interval from 0.60V to 0.95V, the mass activity retention rate at 0.9V is 65.9%, which indicates that the catalyst has higher stability.
Example 2
The present example was used to investigate the effect of different heat treatment temperatures on the performance of the prepared platinum-based catalyst, and specifically, the heat treatment temperature in step 4) of example 1 was adjusted to 800 ℃, 900 ℃, 1000, 1100 ℃, and the rest of the steps were performed in accordance with example 1 to prepare the platinum-based catalyst of the present example.
The performance of the platinum-based catalyst was tested in a three-electrode system, the counter electrode was a carbon rod, the reference electrode was a hydrogen standard, and the working electrode was a rotating diskElectrode, test electrolyte was 0.1M HClO 4 The results are shown in Table 1 and FIG. 8.
TABLE 1 comparison of the Performance of platinum-based catalysts prepared at different heat treatment temperatures
As can be seen from table 1, the different heat treatment temperatures have a significant effect on the performance of the prepared catalyst, and at lower temperatures, rare earth gadolinium cannot diffuse into the platinum alloy with a thermodynamic energy barrier, so the performance is poor; with further temperature rise, gadolinium diffuses into the platinum alloy lattice, and the performance is greatly improved. When the temperature is too high, the carbon carrier is destroyed, the platinum alloy particles are agglomerated, and the performance is lowered.
Example 3
The present example was used to investigate the effect of different metal particle loadings on the performance of the prepared platinum-based catalyst, and specifically, the amount of metal salt added in step 3) of example 1 was adjusted so that the mass percentage of platinum relative to the mass percentage of carbon support was 5wt%,15wt%,25wt%,35wt%,50wt%, and the rest of the procedure was as described in example 1, to prepare the platinum-based catalyst of the present example.
The performance of the platinum-based catalyst was tested in a three-electrode system, the counter electrode was a carbon rod, the reference electrode was a hydrogen standard, the working electrode was a rotating disk electrode, and the test electrolyte was 0.1M HClO 4 The results are shown in Table 2.
TABLE 2 comparison of Performance of platinum-based catalysts made with different nanoparticle loadings
Different metal particle loadings have a significant impact on the performance of the resulting catalyst, with too few active sites and poor performance when the particle loading is low; when the loading is too high, the particles are prone to agglomeration and therefore a suitable loading is required to obtain optimal performance.
Example 4
The present example was used to investigate the effect of a different second metal particle element species on the performance of the prepared platinum-based catalyst, and specifically, the nickel chloride solution in step 3) of example 1 was adjusted to be cobalt chloride solution, ferric chloride solution, and the rest of the steps were performed in the process described in example 1, to prepare the platinum-based catalyst of the present example.
The performance of the platinum-based catalyst was tested in a three-electrode system, the counter electrode was a carbon rod, the reference electrode was a hydrogen standard, the working electrode was a rotating disk electrode, and the test electrolyte was 0.1M HClO 4 The results are shown in Table 3.
TABLE 3 comparison of the Performance of platinum-based catalysts made from different second Metal nanoparticle element species
As can be seen from Table 3, the different second metal particle element species has a significant effect on the performance of the prepared catalyst due to Pt 3 Fe,Pt 3 Co,Pt 3 The phase transition temperatures of Ni and gadolinium are different, and the rare earth doped Pt3Ni has a certain influence on the doping of rare earth gadolinium, and the research shows that the rare earth doped Pt3Ni has the best performance.
In summary, the invention realizes atomic-level dispersion of rare earth gadolinium on a porous carbon substrate through a metal-organic framework (MOF) derivatization strategy, provides abundant anchor sites for nucleation growth of platinum-based alloy, and ensures strong coupling between rare earth and platinum. Rare earth gadolinium is diffused into the lattices of platinum-based alloy particles by a high-temperature heat treatment method, meanwhile, agglomeration of particles under a high-temperature condition is inhibited by utilizing the limiting effect of porous carbon, the size of the formed platinum-based alloy particles is smaller, and the higher noble metal utilization rate is ensured. The preparation method is simple, low in cost and good in reproducibility, and compared with the existing commercial catalyst, the platinum-based alloy catalyst prepared based on the method is lower in noble metal consumption, higher in catalytic activity and better in stability.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (10)
1. A rare earth gadolinium doped high stability platinum-based catalyst is characterized in that: comprises a carbon carrier rich in atomic dispersion gadolinium, and a first metal nanoparticle and a second metal nanoparticle loaded on the surface of the carbon carrier;
the first metal nano particles are platinum, the second metal nano particles comprise one or more of iron, cobalt and nickel, the total loading amount of the metal nano particles is 5-50wt%, and the average particle size is less than 4.50nm.
2. The method for preparing the rare earth gadolinium doped high stability platinum based catalyst according to claim 1, wherein the method comprises the steps of: comprising the steps of (a) a step of,
dissolving metal gadolinium salt and 1,3, 5-benzene tricarboxylic acid in a mixed solvent of water and N, N-dimethylformamide, heating and stirring, centrifugally separating, washing and drying to obtain a white solid, wherein the molar ratio of the metal gadolinium salt to the 1,3, 5-benzene tricarboxylic acid is 3:1-1:1;
performing heat treatment on the white solid in an inert gas atmosphere, and cooling to room temperature to obtain a carbon carrier rich in atomic-level dispersed gadolinium sites;
dispersing a carbon carrier in ultrapure water, adding a metal salt solution, stirring overnight, and performing rotary steaming treatment to obtain a catalyst precursor, wherein the mass of metal in the metal salt is 5-50wt% compared with the addition amount of the carbon carrier;
and carrying out heat treatment on the catalyst precursor in argon-hydrogen mixed gas, cooling, and then sequentially carrying out acid washing, suction filtration and drying to obtain the rare earth gadolinium doped high-stability platinum-based catalyst.
3. The method for preparing the rare earth gadolinium doped high stability platinum based catalyst according to claim 2, wherein the method comprises the steps of: the metal gadolinium salt comprises one of gadolinium chloride hexahydrate and gadolinium nitrate hexahydrate.
4. The method for preparing the rare earth gadolinium doped high stability platinum based catalyst according to claim 2, wherein the method comprises the steps of: the metal salt solution comprises a first metal salt solution and a second metal salt solution, wherein the first metal salt solution is a chloroplatinic acid aqueous solution, and the second metal salt solution comprises one or more of ferric chloride, cobalt chloride and nickel chloride aqueous solution.
5. The method for preparing the rare earth gadolinium doped high stability platinum based catalyst according to claim 2, wherein the method comprises the steps of: the heating temperature of the heating and stirring is 50-100 ℃ and the heating time is 3-6 h.
6. The method for preparing the rare earth gadolinium doped high stability platinum based catalyst according to claim 2, wherein the method comprises the steps of: the heat treatment is carried out in an inert gas atmosphere, wherein the inert gas comprises argon or nitrogen, the heating rate of the heat treatment is 1-10 ℃/min, the temperature is 800-1000 ℃, and the time is 0.5-3 h.
7. The method for preparing the rare earth gadolinium doped high stability platinum based catalyst according to claim 2, wherein the method comprises the steps of: the catalyst precursor is subjected to heat treatment in an argon-hydrogen mixed gas, wherein the volume content of hydrogen in the argon-hydrogen mixed gas is 5-10 vol%.
8. The method for preparing the rare earth gadolinium doped high stability platinum based catalyst according to claim 7, wherein the method comprises the steps of: the heating rate of the heat treatment is 0.5-10 ℃/min, the temperature is 600-1100 ℃ and the time is 1-4 h.
9. The method for preparing the rare earth gadolinium doped high stability platinum based catalyst according to claim 2, wherein the method comprises the steps of: the acid treatment solution for acid washing is perchloric acid or dilute hydrochloric acid solution with the concentration of 0.1-1 mol/L.
10. Use of a rare earth gadolinium doped high stability platinum based catalyst according to claim 1 as a fuel cell cathode material.
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