CN117976926B - Preparation method of durable Pt-M alloy catalyst - Google Patents
Preparation method of durable Pt-M alloy catalyst Download PDFInfo
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- CN117976926B CN117976926B CN202410363910.XA CN202410363910A CN117976926B CN 117976926 B CN117976926 B CN 117976926B CN 202410363910 A CN202410363910 A CN 202410363910A CN 117976926 B CN117976926 B CN 117976926B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 239000000956 alloy Substances 0.000 title claims abstract description 38
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 17
- 229910052737 gold Inorganic materials 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims description 58
- 239000011259 mixed solution Substances 0.000 claims description 44
- 239000007787 solid Substances 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 229910052723 transition metal Inorganic materials 0.000 claims description 14
- 239000010931 gold Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000007710 freezing Methods 0.000 claims description 8
- 230000008014 freezing Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- -1 transition metal salt Chemical class 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 12
- 239000002245 particle Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 150000001768 cations Chemical class 0.000 abstract description 3
- 239000011865 Pt-based catalyst Substances 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 239000006185 dispersion Substances 0.000 description 12
- 238000004090 dissolution Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 150000004687 hexahydrates Chemical class 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 5
- 229910000531 Co alloy Inorganic materials 0.000 description 4
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910002837 PtCo Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000914 Mn alloy Inorganic materials 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- UQLLJPLUKUGLNR-UHFFFAOYSA-L manganese(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Mn+2] UQLLJPLUKUGLNR-UHFFFAOYSA-L 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 239000011345 viscous material Substances 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
- H01M4/92—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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- 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
-
- 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)
- Inert Electrodes (AREA)
Abstract
The invention relates to a preparation method of a durable Pt-M alloy catalyst, and belongs to the technical field of fuel cell catalysts. Some studies have been made in the prior art to improve the durability of Pt-based catalysts, with methods mainly focused on the treatment by high temperature, or doping, or surface coating. The high-temperature heat treatment can lead to the growth and agglomeration of catalyst particles, and the catalytic activity of the catalyst is obviously reduced; doping cannot prevent loss of internal alloy components; the surface coating directly covers the active sites of the catalyst, resulting in reduced activity. According to the invention, the Pt atoms or the positions occupied by the mixed atoms of Pt and Au during the reaction of the alloy components are utilized to lock the internal alloy components, so that the outflow of metal cations is greatly inhibited, and the durability of the catalyst is remarkably improved.
Description
Technical Field
The invention belongs to the technical field of fuel cell catalysts, and relates to a preparation method of a durable Pt-M alloy catalyst.
Background
The advent of Proton Exchange Membrane Fuel Cells (PEMFCs) and fuel cell power plants marked the advent of the hydrogen energy era. Proton exchange membrane fuel cells are indispensable catalysts for catalysis in this process by directly converting chemical energy in hydrogen and oxygen into electrical energy. In recent years, research on proton exchange membrane fuel cell catalysts has focused on how to study the morphology, size and composition of platinum-based nanoparticles to improve the activity and durability of the catalysts. The durability of the Pt-M alloy catalyst is to inhibit the dissolution of the alloy component M. The eluted M 2+ will cause the catalytic activity of the catalyst particles to decrease, and the cations entering the ionomer will occupy the proton position, resulting in a significant decrease in proton conductivity and affecting the performance of the fuel cell.
Some studies have been made in the prior art to improve the durability of Pt-based catalysts, with methods mainly focused on the treatment by high temperature, or doping, or surface coating. The high-temperature heat treatment can lead to the growth and agglomeration of catalyst particles, and the catalytic activity of the catalyst is obviously reduced; doping cannot prevent loss of internal alloy components; the surface coating directly covers the active sites of the catalyst, resulting in reduced activity.
Disclosure of Invention
The invention aims to provide a preparation method of a durable Pt-M alloy catalyst, which has the characteristic of good durability.
The high platinum loading and high cost are the difficult problems leading to the large-scale popularization of fuel cell automobiles, and the reason is mainly due to the low catalytic activity of the platinum-carbon catalyst commonly used in the fuel cells at present. The second transition metal (such as Co, mn, ni and the like) can be introduced to form an alloy with Pt, the electron and the geometric structure of Pt are regulated, the catalytic activity of the catalyst is obviously improved, the activity can be improved by 2-3 times, and the platinum consumption of the fuel cell can be reduced by more than 50%. However, since the fuel cell is in an acidic, high-potential and high-oxidability environment, transition metal M in the Pt-M alloy can be gradually dissolved out in the long-time operation process, so that on one hand, the activity of the catalyst is reduced, and on the other hand, the dissolution of transition metal ions can also cause pollution of a proton exchange membrane, thereby obviously reducing the performance of the fuel cell and prolonging the service life. Therefore, it is important to improve the stability of Pt-M alloy catalysts.
The aim of the invention can be achieved by the following technical scheme:
A preparation method of a durable Pt-M alloy catalyst comprises the following steps of,
S1: the carbon carrier, the hexahydrated chloroplatinic acid and the transition metal salt are mixed according to the mass ratio of 1: (2.6 to 3.4): (0.3-1.6) adding the mixture into deionized water, stirring and uniformly mixing to obtain a mixed solution A;
S2: continuously stirring the mixed solution A, heating to 90-120 ℃ at the same time, carrying out evaporation reaction on the mixed solution, stopping heating when the mixed solution is evaporated to a viscous state, cooling to room temperature, carrying out freeze drying treatment in a freeze dryer, firstly carrying out freezing treatment on the mixed solution for 10-15 min by using liquid nitrogen, then drying the mixed solution frozen to be solid at the temperature of-70 to-50 ℃ in a vacuum state for 24h, and obtaining black solid powder B after freeze drying;
S3: carrying out reduction treatment on the black solid powder B prepared in the step S2 in a reducing gas atmosphere, wherein the reaction temperature is 700-900 ℃, the reaction time is 1-3 hours, and after the reaction is finished, slowly cooling to room temperature at a speed of 5 ℃/min to obtain solid powder C;
S4: dissolving chloroplatinic acid and chloroauric acid in deionized water to obtain a mixed solution, deoxidizing the mixed solution of chloroplatinic acid and chloroauric acid by using inert gas, dispersing solid powder C prepared in S3 in the treated mixed solution, reacting for 1-5 h at the temperature of 30-60 ℃, filtering and washing the mixed solution obtained by the reaction, and drying for 12h at the temperature of 100 ℃ in nitrogen atmosphere to obtain the Pt-M alloy catalyst.
Further, the transition metal salt in the step S1 is one or more of chloride, nitrate, acetate, sulfate and acetylacetonate.
Further, the transition metal is one of cobalt, nickel, manganese, chromium, copper and palladium.
Further, the solid content of carbon in the mixture in a viscous state obtained by the evaporation reaction in the step S2 is 10-40 wt%.
Further, the reducing gas in the step S3 is one of hydrogen, a hydrogen-argon mixture, a hydrogen-nitrogen mixture and carbon monoxide.
Further, the concentration of the mixed solution of chloroplatinic acid and chloroauric acid in the step S4 is 1-2 wt%.
Further, the molar ratio of platinum to gold in the chloroplatinic acid and chloroauric acid mixed solution is 1:1.
Further, the inert gas in S4 is one of nitrogen, helium and argon.
According to the invention, the mixed solution of carbon powder, platinum salt and transition metal salt is subjected to rotary evaporation, the viscosity of the mixed solution is controlled, the subsequent freeze-drying material is unevenly distributed due to excessive water, the water is too little, the salt in the material is likely to segregate, and the material is also unevenly distributed. And then freeze drying is combined with a proper viscous material, and metal ions are in-situ and uniformly fixed in a carbon carrier through quenching of liquid nitrogen, so that the Pt-M alloy particles which are uniformly distributed can be obtained after subsequent reduction.
The transition metal dissolution pore canal refers to that in the alloy material, transition metal elements can be dissolved out from crystal lattices to form pore canals, and the pore canals can enhance the strength of the material and improve the conductivity. Platinum and gold have good chemical stability and corrosion resistance, and can play a role in enhancing the performance of the alloy material. Therefore, platinum and gold can pass through the transition metal dissolution pore canal occupying the surface layer to enhance the performance of the alloy and increase the activity and selectivity of the catalyst.
The invention adopts an in-situ replacement method to enable the metal M with higher activity in the Pt-M to replace proper amount of Pt and Au on the surface of the alloy particles. In the high-temperature reduction and alloying process, part of transition metal M is distributed on the surface of Pt-M alloy particles, and the part of transition metal M has high activity and is easy to dissolve and oxidize in the fuel cell under the acidic condition. Therefore, the invention starts from the point, and makes full use of the inert atmosphere protection solution of chloroplatinic acid and chloroauric acid after deoxidization by M reduction in the surface metal state. Thus, the position originally occupied by M is occupied by Pt or Au, and the Pt or Au has high stability, can further inhibit the dissolution of M in the Pt-M alloy after being deposited on the surface, and can keep the activity and durability of the catalyst for a long time. It is worth pointing out that the deoxidization treatment in the invention is very critical to the immersion uniformity and compactness of Pt and Au, and the condition that the deoxidization is not performed or is not completed can lead to M preferential oxidation and dissolution under the oxygen condition, so that the deposited Pt is not compact enough, and the M in the alloy runs for a long time, so that the deoxidization process is very critical.
The invention has the beneficial effects that:
According to the invention, the Pt atoms or the positions occupied by the mixed atoms of Pt and Au during the reaction of the alloy components are utilized to lock the internal alloy components, so that the outflow of metal cations is greatly inhibited, and the durability of the catalyst is remarkably improved.
Drawings
The present invention is further described below with reference to the accompanying drawings for the convenience of understanding by those skilled in the art.
FIG. 1 PtCo is a schematic illustration of an alloy catalyst durability improvement;
fig. 2 examples 3 and 4 demonstrate improved performance in a battery for catalyst durability;
FIG. 3 example 4 and comparative example 1 demonstrate improved catalyst durability in batteries;
Fig. 4 example 4 and comparative example 4 demonstrate improved performance in a battery for catalyst durability.
Detailed Description
In order to further illustrate the technical means and effects of the present invention for achieving the intended purpose, referring to the drawings and the preferred embodiments, fig. 1 is a schematic diagram showing the durability improvement of the PtCo alloy catalyst, and it can be known from the figure that the Co is replaced in situ by Pt and Au on the surface, so that the dissolution of Co in the interior can be effectively inhibited, and the specific embodiments, structures, features and effects according to the present invention are described in detail below.
Example 1
S1: weighing 4.0g of carbon powder, 13.3g of chloroplatinic acid hexahydrate and 6.1g of cobalt chloride hexahydrate, adding 100g of deionized water, stirring, dispersing and uniformly mixing at a stirring speed of 1000rpm for 30min to obtain mixed liquid slurry A;
S2: heating the mixed dispersion slurry A to 100 ℃ under stirring to evaporate, observing the state of the slurry, stopping heating until the mixed dispersion becomes sticky, cooling to room temperature to freeze-dry, performing freezing treatment on the mixed liquid for 10-15 min by using liquid nitrogen, and drying the mixed liquid frozen to solid at-70 to-50 ℃ under vacuum for 24h to obtain black solid powder B;
S3: treating black solid powder B in an atmosphere protection furnace at 800 ℃ in 5% hydrogen-argon mixed gas for 2 hours, and slowly cooling to room temperature at 5 ℃/min after the reaction is finished to obtain black solid powder C;
S4: dissolving chloroplatinic acid and chloroauric acid in deionized water to prepare a mixed solution with the mass concentration of 1wt%, wherein the atomic ratio of the chloroplatinic acid to the chloroauric acid is 1: and 1, carrying out deoxidization treatment on the prepared mixed solution by using nitrogen, dispersing black solid powder C in the mixed solution, stirring and reacting for 2 hours at 60 ℃, filtering, cleaning, drying at 100 ℃ for 12 hours in a nitrogen atmosphere, and drying to obtain the durable PtCo alloy catalyst.
In this example, the Pt content was 48wt% and the Co content was 14.4wt%.
Example 2
S1: weighing 4.7g of carbon powder, 13.3g of chloroplatinic acid hexahydrate and 3.05g of cobalt chloride hexahydrate, adding 100g of deionized water, stirring, dispersing and uniformly mixing at a stirring speed of 1000rpm for 30min to obtain mixed liquid slurry A;
S2: heating the mixed dispersion slurry A to 100 ℃ under stirring to evaporate, observing the state of the slurry, stopping heating until the mixed dispersion becomes sticky, cooling to room temperature to freeze-dry, freezing the mixed liquid for 10-15 min by using liquid nitrogen, and drying the mixed liquid frozen to solid at-70 to-50 ℃ under vacuum for 24h to obtain black solid powder B;
S3: treating black solid powder B in an atmosphere protection furnace at 800 ℃ in 5% hydrogen-argon mixed gas for 2 hours, and slowly cooling to room temperature at 5 ℃/min after the reaction is finished to obtain black solid powder C;
S4: dissolving chloroplatinic acid and chloroauric acid in deionized water to prepare a mixed solution with the mass concentration of 1wt%, wherein the atomic ratio of the chloroplatinic acid to the chloroauric acid is 1: and 1, carrying out deoxidization treatment on the prepared mixed solution by using nitrogen, dispersing black solid powder C in the mixed solution, stirring and reacting for 2 hours at 60 ℃, filtering, cleaning, drying at 100 ℃ for 12 hours in a nitrogen atmosphere, and drying to obtain the durable Pt 2 Co alloy catalyst.
In this example, the Pt content was 48wt% and the Co content was 7.2wt%.
Example 3
S1: weighing 5.0g of carbon powder, 13.3g of chloroplatinic acid hexahydrate and 2.03g of cobalt chloride hexahydrate, adding 100g of deionized water, stirring, dispersing and uniformly mixing at a stirring speed of 1000rpm for 30min to obtain mixed liquid slurry A;
s2: heating the mixed dispersion slurry A to 100 ℃ under stirring to evaporate, observing the state of the slurry, stopping heating until the mixed dispersion becomes sticky, cooling to room temperature to freeze-dry, performing freezing treatment on the mixed liquid for 10-15 min by using liquid nitrogen, and drying the mixed liquid frozen to solid at-70 to-50 ℃ under vacuum for 24h to obtain black solid powder B;
S3: treating black solid powder B in an atmosphere protection furnace at 800 ℃ in 5% hydrogen-argon mixed gas for 2 hours, and slowly cooling to room temperature at 5 ℃/min after the reaction is finished to obtain black solid powder C;
S4: dissolving chloroplatinic acid and chloroauric acid in deionized water to prepare a mixed solution with the mass concentration of 1wt%, wherein the atomic ratio of the chloroplatinic acid to the chloroauric acid is 1: and 1, carrying out deoxidization treatment on the prepared mixed solution by using nitrogen, dispersing black solid powder C in the mixed solution, stirring and reacting for 2 hours at 60 ℃, filtering, cleaning, drying at 100 ℃ for 12 hours in a nitrogen atmosphere, and drying to obtain the durable Pt 3 Co alloy catalyst.
In this example, the Pt content was 48wt% and the Co content was 4.7wt%.
Example 4
The durability of the Pt 3 Co alloy catalyst is improved as follows, the Pt content is 48 weight percent, the Co content is 4.7 weight percent, and the method specifically comprises the following steps:
s1: weighing 5.0g of carbon powder, 13.3g of chloroplatinic acid hexahydrate and 2.03g of cobalt chloride hexahydrate, adding 100g of deionized water, stirring, dispersing and uniformly mixing at a stirring speed of 1000rpm for 30min to obtain mixed liquid slurry A;
s2: heating the mixed dispersion slurry A to 100 ℃ under stirring to evaporate, observing the state of the slurry, stopping heating until the mixed dispersion becomes sticky, cooling to room temperature to freeze-dry, performing freezing treatment on the mixed liquid for 10-15 min by using liquid nitrogen, and drying the mixed liquid frozen to solid at-70 to-50 ℃ under vacuum for 24h to obtain black solid powder B;
S3: treating black solid powder B in an atmosphere protection furnace at 800 ℃ in 5% hydrogen-argon mixed gas for 2 hours, and slowly cooling to room temperature at 5 ℃/min after the reaction is finished to obtain black solid powder C;
S4: dissolving chloroplatinic acid and chloroauric acid in deionized water to prepare a mixed solution with the mass concentration of 2wt%, wherein the atomic ratio of the chloroplatinic acid to the chloroauric acid is 1: and 1, carrying out deoxidization treatment on the prepared mixed solution by using nitrogen, dispersing black solid powder C in the mixed solution, stirring and reacting for 2 hours at 60 ℃, filtering, cleaning, drying at 100 ℃ for 12 hours in a nitrogen atmosphere, and drying to obtain the durable Pt 3 Co alloy catalyst.
Example 5
The durability of the Pt 3 Ni alloy catalyst is improved as follows, the Pt content is 48wt% and the Ni content is 5.2wt%, and the method specifically comprises the following steps:
s1: weighing 5.0g of carbon powder, 13.3g of chloroplatinic acid hexahydrate and 2.03g of nickel chloride hexahydrate, adding 100g of deionized water, stirring, dispersing and uniformly mixing at a stirring speed of 1000rpm for 30min to obtain mixed liquid slurry A;
s2: heating the mixed dispersion slurry A to 100 ℃ under stirring to evaporate, observing the state of the slurry, stopping heating until the mixed dispersion becomes sticky, cooling to room temperature to freeze-dry, performing freezing treatment on the mixed liquid for 10-15 min by using liquid nitrogen, and drying the mixed liquid frozen to solid at-70 to-50 ℃ under vacuum for 24h to obtain black solid powder B;
S3: treating black solid powder B in an atmosphere protection furnace at 800 ℃ in 5% hydrogen-argon mixed gas for 2 hours, and slowly cooling to room temperature at 5 ℃/min after the reaction is finished to obtain black solid powder C;
S4: dissolving chloroplatinic acid and chloroauric acid in deionized water to prepare a mixed solution with the mass concentration of 2wt%, wherein the atomic ratio of the chloroplatinic acid to the chloroauric acid is 1: and 1, carrying out deoxidization treatment on the prepared mixed solution by using nitrogen, dispersing black solid powder C in the mixed solution, stirring and reacting for 2 hours at 60 ℃, filtering, cleaning, drying at 100 ℃ for 12 hours in a nitrogen atmosphere, and drying to obtain the durable Pt 3 Ni alloy catalyst.
In this example, the Pt content was 48wt% and the Ni content was 5.2wt%.
Example 6
The durability of the Pt 3 Mn alloy catalyst is improved as follows, the Pt content is 48 weight percent, the Ni content is 5.2 weight percent, and the method specifically comprises the following steps:
S1: weighing 5.0g of carbon powder, 13.3g of chloroplatinic acid hexahydrate and 1.69g of manganese chloride hexahydrate, adding 100g of deionized water, stirring, dispersing and uniformly mixing at a stirring speed of 1000rpm for 30min to obtain mixed liquid slurry A;
s2: heating the mixed dispersion slurry A to 100 ℃ under stirring to evaporate, observing the state of the slurry, stopping heating until the mixed dispersion becomes sticky, cooling to room temperature to freeze-dry, performing freezing treatment on the mixed liquid for 10-15 min by using liquid nitrogen, and drying the mixed liquid frozen to solid at-70 to-50 ℃ under vacuum for 24h to obtain black solid powder B;
S3: treating black solid powder B in an atmosphere protection furnace at 800 ℃ in 5% hydrogen-argon mixed gas for 2 hours, and slowly cooling to room temperature at 5 ℃/min after the reaction is finished to obtain black solid powder C;
S4: dissolving chloroplatinic acid and chloroauric acid in deionized water to prepare a mixed solution with the mass concentration of 2wt%, wherein the atomic ratio of the chloroplatinic acid to the chloroauric acid is 1: and 1, carrying out deoxidization treatment on the prepared mixed solution by using nitrogen, dispersing black solid powder C in the mixed solution, stirring and reacting for 2 hours at 60 ℃, filtering, cleaning, drying at 100 ℃ for 12 hours in a nitrogen atmosphere, and drying to obtain the durable Pt 3 Mn alloy catalyst.
In this example, the Pt content was 48wt% and the Ni content was 5.2wt%.
Comparative example 1
The comparative example has a Pt content of 48wt% and a Co content of 4.7wt% and differs from example 4 only in that chloroplatinic acid and chloroauric acid are not added in step4, and the other operations are completely identical.
Comparative example 2
The comparative example has a Pt content of 48wt% and a Co content of 4.7wt% and differs from example 4 only in that in step 4, only 2wt% of chloroplatinic acid was added, and no chloroauric acid was added, and the other operations were completely identical.
Comparative example 3
The comparative example has a Pt content of 48wt% and a Co content of 4.7wt% and differs from example 4 only in that in step 4, only 2wt% of chloroauric acid was added, and no chloroplatinic acid was added, and the other operations were completely identical.
Comparative example 4
The comparative example has a Pt content of 48wt% and a Co content of 4.7wt% and differs from example 4 only in that 10wt% of chloroauric acid and chloroplatinic acid (in excess) were added in step 4, and the other operations were completely identical.
As can be seen from the experiments of the examples and comparative examples,
Fig. 2 shows that examples 3 and 4 have improved durability for the catalyst in the battery, and it can be seen from the figure that example 4 has higher durability than example 3, which may benefit from more Pt and Au on the surface occupying pores in situ during Co elution, effectively inhibiting Co elution inside.
Fig. 3 shows the improved performance of example 4 and comparative example 1 on catalyst durability in the battery, and it can be seen from the figure that example 4 has higher durability than comparative example 1, which may benefit from the surface Pt and Au occupying the pore channels in situ during Co elution, effectively inhibiting the elution of Co inside.
Fig. 4 is a graph showing the improved performance of example 4 and comparative example 4 on catalyst durability in a battery, and it can be seen from the graph that example 4 has higher activity than comparative example 4, which may be due to the deposition of thicker Pt and Au on the surface of comparative example 4, resulting in a decrease in the overall performance of the catalyst.
The present invention is not limited to the above embodiments, but is capable of modification and variation in detail, and other modifications and variations can be made by those skilled in the art without departing from the scope of the present invention.
Claims (8)
1. A preparation method of a durable Pt-M alloy catalyst is characterized in that the catalyst preparation flow is as follows,
S1: the carbon carrier, the hexahydrated chloroplatinic acid and the transition metal salt are mixed according to the mass ratio of 1: (2.6 to 3.4): (0.3-1.6) adding the mixture into deionized water, stirring and uniformly mixing to obtain a mixed solution A;
S2: continuously stirring the mixed solution A, heating to 90-120 ℃ at the same time, carrying out evaporation reaction on the mixed solution, stopping heating when the mixed solution is evaporated to a viscous state, cooling to room temperature, carrying out freeze drying treatment in a freeze dryer, firstly carrying out freezing treatment on the mixed solution for 10-15 min by using liquid nitrogen, then drying the mixed solution frozen to be solid at the temperature of-70 to-50 ℃ in a vacuum state for 24h, and obtaining black solid powder B after freeze drying;
S3: carrying out reduction treatment on the black solid powder B prepared in the step S2 in a reducing gas atmosphere, wherein the reaction temperature is 700-900 ℃, the reaction time is 1-3 hours, and after the reaction is finished, slowly cooling to room temperature at a speed of 5 ℃/min to obtain solid powder C;
S4: dissolving chloroplatinic acid and chloroauric acid in deionized water to obtain a mixed solution, deoxidizing the mixed solution of chloroplatinic acid and chloroauric acid by using inert gas, dispersing solid powder C prepared in S3 in the treated mixed solution, reacting for 1-5 h at the temperature of 30-60 ℃, filtering and washing the mixed solution obtained by the reaction, and drying for 12h at the temperature of 100 ℃ in nitrogen atmosphere to obtain the Pt-M alloy catalyst.
2. The method for preparing a durable Pt-M alloy catalyst according to claim 1, wherein the transition metal salt in S1 is one or more of chloride, nitrate, acetate, sulfate, acetylacetonate.
3. The method for preparing a durable Pt-M alloy catalyst according to claim 2, wherein the transition metal is one of cobalt, nickel, manganese, chromium, copper, and palladium.
4. The method for preparing a durable Pt-M alloy catalyst according to claim 1, wherein the solid content of carbon in the mixture in a viscous state obtained by the evaporation reaction in S2 is 10-40 wt%.
5. The method for preparing a durable Pt-M alloy catalyst according to claim 1, wherein the reducing gas in S3 is one of hydrogen, a hydrogen-argon mixture, a hydrogen-nitrogen mixture, and carbon monoxide.
6. The method for preparing a durable Pt-M alloy catalyst according to claim 1, wherein the concentration of the mixed solution of chloroplatinic acid and chloroauric acid in S4 is 1wt% to 2wt%.
7. The method for preparing a durable Pt-M alloy catalyst according to claim 6, wherein the molar ratio of platinum to gold in the mixed solution of chloroplatinic acid and chloroauric acid is 1:1.
8. The method for preparing a durable Pt-M alloy catalyst according to claim 1, wherein the inert gas in S4 is one of nitrogen, helium and argon.
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