CN112403463A - Pt-based perovskite catalyst and preparation method thereof - Google Patents
Pt-based perovskite catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000010306 acid treatment Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000008139 complexing agent Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 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 1
- 238000011946 reduction process Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 238000001354 calcination Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000446 fuel Substances 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
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- 238000005406 washing Methods 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910018089 Al Ka Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910017414 LaAl Inorganic materials 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 238000010304 firing Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- H—ELECTRICITY
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- 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
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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- H—ELECTRICITY
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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a Pt-based perovskite catalyst and a preparation method thereof. The method comprises the following steps: dispersing Pt source and soluble salt containing A, B element in water, adding complexing agent, mixing and stirring, drying and high-temperature roasting to obtain ABxPt(1‑x)O3A perovskite; will ABxPt(1‑x)O3And carrying out acid treatment and reduction on the perovskite to obtain the Pt-based perovskite catalyst. According to the invention, through selecting a proper roasting temperature and combining acid treatment, Pt atoms can be segregated on the surface of the catalyst, and the content of Pt exposed on the surface is obviously improved, so that the utilization rate of Pt is improved, and the catalytic activity of the Pt-based perovskite catalyst is finally improved.
Description
Technical Field
The invention relates to the technical field of preparation of fuel cell catalysts, in particular to a Pt-based perovskite catalyst and a preparation method thereof.
Background
The hydrogen fuel cell is a power generation device which directly converts chemical energy of fuel into electric energy through electrode reaction, has the characteristics of small environmental pollution, low noise and the like, and is known as a clean and efficient power generation technology preferred in the 21 st century. Such efficient and clean power generation systems that directly convert chemical energy into electrical energy continuously have received much attention since their inception. Catalysts with high catalytic activity and stability are essential in the redox process of hydrogen fuel cells.
Pt-based perovskite-type catalysts are considered to be a new type of hydrogen fuel cell catalyst with comparative potential in the future. At present, corresponding precursors are generally prepared in advance by a coprecipitation method and a sol-gel method, and then the Pt-based perovskite catalyst is obtained by roasting. After firing, Pt as a main active component is relatively uniformly dispersed in the bulk phase of perovskite, and the surface-exposed Pt component is small. However, in the catalytic reaction of the hydrogen fuel cell, only a few atomic layers on the surface can participate in the catalytic reaction, the internal components cannot play a catalytic role, the content of exposed Pt on the surface is low, the utilization rate of Pt is low, and the improvement of the oxygen reduction activity of the cathode of the hydrogen fuel cell is not facilitated.
Disclosure of Invention
In view of the above, it is necessary to provide a Pt-based perovskite catalyst and a preparation method thereof, so as to solve the technical problem of low Pt utilization rate of the existing Pt-based perovskite catalyst in the prior art.
A first aspect of the present invention provides a method for preparing a Pt-based perovskite-type catalyst, comprising the steps of:
dispersing Pt source and soluble salt containing A, B element in water, adding complexing agent, mixing and stirring, drying and high-temperature roasting to obtain ABxPt(1-x)O3A perovskite;
will ABxPt(1-x)O3And carrying out acid treatment and reduction on the perovskite to obtain the Pt-based perovskite catalyst.
A second aspect of the present invention provides a Pt-based perovskite-type catalyst obtained by the method for preparing a Pt-based perovskite-type catalyst provided by the first aspect of the present invention.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, through selecting a proper roasting temperature and combining acid treatment, Pt atoms can be segregated on the surface of the catalyst, and the content of Pt exposed on the surface is obviously improved, so that the utilization rate of Pt is improved, and the catalytic activity of the Pt-based perovskite catalyst is finally improved.
Drawings
FIG. 1 is a process flow diagram of one embodiment of a method of preparing a Pt-based perovskite catalyst provided by the present invention;
FIG. 2 is a TEM image of a Pt-based perovskite-type catalyst (LCP-1000-H90) provided in example 1 of the present invention;
FIG. 3 is a TEM image of Pt-based perovskite-type catalysts (LCP-650-H90 and LCP-850-H90 in order from left to right) provided in examples 4 and 5 of the present invention;
FIG. 4 is a TEM image of Pt-based perovskite-type catalysts (LCP-1000 and LCP-1000-H120 in order from left to right) provided in comparative example 1 and example 12 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
A first aspect of the present invention provides a method for preparing a Pt-based perovskite-type catalyst, comprising the steps of:
s1 dispersing Pt source and soluble salt containing A, B elements in water, adding complexing agent, mixing and stirring, drying and roasting at high temperature to obtain ABxPt(1-x)O3A perovskite; the element A is at least one of lanthanum (La), praseodymium (Pr) and cerium (Ce), and the soluble salt used by the element A is nitrate, chloride or acetate containing at least one of lanthanum, praseodymium and cerium; the element B is at least one of cobalt (Co), manganese (Mn) and aluminum (Al), and further soluble salt used by the element B is nitrate, chloride or acetate containing at least one of cobalt, manganese and aluminum; the Pt source is at least one of chloroplatinic acid and ammonium chloroplatinate; x is the molar ratio of the B element to the (B + Pt) element, and the range of x is 0.7-0.95, and preferably 0.8; the complexing agent is citric acid. The ratio of the total molar amount of the Pt source and soluble salt containing A, B element to the molar amount of the complexing agent is 1 (0.6-1.2), and preferably 1: 1; furthermore, the dosage ratio of the soluble salt used by the element A to water is (0.3-0.4) mol: 1L. The mixing and stirring time is 30-60 min; the drying temperature is 90-120 ℃, and the drying time is 15-30 h; in the process, a perovskite structure is formed through high-temperature roasting, the high-temperature roasting temperature is 650-1300 ℃, along with the increase of the roasting temperature, the surface Pt content rapidly rises firstly, then slowly falls, the specific surface area gradually falls, and the fact that the higher roasting temperature is beneficial to improving the surface Pt content is shown, but the higher roasting temperature can cause the specific surface to be active on the contraryLow, but not beneficial to the promotion of catalytic activity; preferably 850-1100 ℃, and further 1000 ℃, wherein the range can simultaneously give consideration to higher surface Pt content and higher specific surface area; the high-temperature roasting time is 3-5 h, preferably 4 h.
S2 mixing the above ABxPt(1-x)O3Carrying out acid treatment and reduction on the perovskite to obtain a Pt-based perovskite catalyst; wherein, the acid selected in the acid treatment process is hydrochloric acid or nitric acid, the molar concentration is 3-6 mol/L, and ABxPt(1-x)O3The solid-to-liquid ratio of perovskite to acid is 1 g: (5-10) ml, preferably 1 g: 8ml of the solution; the acid treatment time is 15-120 min, the surface Pt content also shows a trend of rising firstly and then falling along with the increase of the acid treatment time, meanwhile, the acid treatment time can slightly improve a specific table, which indicates that the higher acid treatment time is more beneficial to improving the surface Pt content and the specific surface area, and further improving the catalytic activity, but the excessive acid treatment can cause slight agglomeration, so that the surface Pt content is reduced, preferably, the acid treatment time is 60-120 min, further 90-120 min, and further 90 min; during the reduction, the atmosphere selected was a mixture of nitrogen and hydrogen, further 10% H2+90％N2(ii) a The reduction temperature is 120-180 ℃, further 150 ℃, and the reduction time is 20-40 min, further 30 min.
Compared with the conventional Pt-based perovskite catalyst, the method has the advantages that by selecting a proper roasting temperature and combining acid treatment, Pt atoms can be segregated on the surface of the catalyst, the Pt content exposed on the surface is obviously improved, the utilization rate of Pt is improved, and the catalytic activity of the Pt-based perovskite catalyst is improved.
A second aspect of the present invention provides a Pt-based perovskite-type catalyst obtained by the method for preparing a Pt-based perovskite-type catalyst provided by the first aspect of the present invention.
Example 1
(1) Dissolving 0.1mol of lanthanum nitrate, 0.08mol of cobalt nitrate and 0.02mol of chloroplatinic acid in 300ml of deionized water, adding 0.2mol of citric acid, stirring for 60min, then placing into a 110 ℃ oven for 20h for drying, and then baking at 1000 DEG CFiring for 4h to obtain LaCo0.8Pt0.2O3A perovskite;
(2) mixing LaCo0.8Pt0.2O3Soaking perovskite in 5mol/L nitric acid for 90min (solid-to-liquid ratio is 1 g: 8ml), washing with deionized water, vacuum filtering, drying, and adding 10% H2+90％N2Reducing for 30min at 150 ℃ in atmosphere to obtain Pt/LaCo with Pt particles distributed on the surface0.8Pt0.2O3Perovskite catalyst (LCP-1000-H90 below).
Example 2
(1) Dissolving 0.1mol of lanthanum nitrate, 0.095mol of manganese nitrate and 0.005mol of chloroplatinic acid in 300ml of deionized water, adding 0.12mol of citric acid, stirring for 30min, then placing in a 90 ℃ oven for 30h for drying, and then roasting for 3h at 1000 ℃ to obtain LaMn0.95Pt0.05O3A perovskite;
(2) mixing LaMn0.95Pt0.05O3Soaking perovskite in 6mol/L nitric acid for 90min (solid-to-liquid ratio is 1 g: 5ml), washing with deionized water, vacuum filtering, drying, and adding 10% H2+90％N2Reducing for 40min at 120 ℃ in atmosphere to obtain Pt/LaMn with Pt particles distributed on the surface0.95Pt0.05O3Perovskite catalyst (hereinafter LMP-1000-H90).
Example 3
(1) Dissolving 0.1mol of lanthanum nitrate, 0.07mol of aluminum nitrate and 0.03mol of chloroplatinic acid in 300ml of deionized water, adding 0.24mol of citric acid, stirring for 45min, then placing in a 120 ℃ oven for 15h for drying, and then roasting for 5h at 1000 ℃ to obtain LaAl0.7Pt0.3O3A perovskite;
(2) mixing LaAl0.7Pt0.3O3Soaking in 3mol/L nitric acid for perovskite for 90min (solid-to-liquid ratio is 1 g: 10ml), washing with deionized water, vacuum filtering, drying, and adding 10% H2+90％N2Reducing for 20min at 180 ℃ in the atmosphere to obtain Pt/LaAl with Pt particles distributed on the surface0.7Pt0.3O3Perovskite catalyst (hereinafter LAP-1000-H90).
Example 4
The only difference compared with example 1 is that in example 4, the calcination temperature is 650 deg.C, and the obtained Pt/LaCo0.8Pt0.2O3The perovskite catalyst is hereinafter designated LCP-650-H90.
Example 5
The only difference compared with example 1 is that in example 5, the calcination temperature is 850 deg.C, and the obtained Pt/LaCo0.8Pt0.2O3The perovskite catalyst is hereinafter LCP-850-H90.
Example 6
The only difference compared with example 1 is that in example 6, the calcination temperature is 1100 ℃, and the Pt/LaCo obtained0.8Pt0.2O3The perovskite catalyst is hereinafter designated LCP-1100-H90.
Example 7
The only difference compared with example 1 is that in example 7, the calcination temperature was 1200 deg.C, and the Pt/LaCo obtained0.8Pt0.2O3The perovskite catalyst is hereinafter designated LCP-1200-H90.
Example 8
The only difference compared with example 1 is that in example 8, the calcination temperature is 1300 ℃ and the Pt/LaCo obtained0.8Pt0.2O3The perovskite catalyst is hereinafter LCP-1300-H90.
Example 9
The only difference compared to example 1 is that in example 9, the acid treatment time was 15min, and the Pt/LaCo obtained0.8Pt0.2O3The perovskite catalyst is hereinafter designated LCP-1000-H15.
Example 10
The only difference compared with example 1 is that in example 10, the acid treatment time was 30min, and the obtained Pt/LaCo0.8Pt0.2O3The perovskite catalyst is hereinafter designated LCP-1000-H30.
Example 11
The only difference compared with example 1 is that in example 11, the acid treatment time was 60min, and the obtained Pt/LaCo0.8Pt0.2O3The perovskite catalyst is hereinafter designated LCP-1000-H60.
Example 12
The only difference compared with example 1 is that in example 12, the acid treatment time was 120min, and the obtained Pt/LaCo0.8Pt0.2O3The perovskite catalyst is hereinafter LCP-1000-H120.
Comparative example 1
The only difference compared with example 1 is that in comparative example 1, Pt/LaCo is obtained without acid treatment and directly reduced after high temperature roasting0.8Pt0.2O3The perovskite catalyst is hereinafter LCP-1000.
Test group 1
The catalysts obtained in examples 1 to 12 and comparative example 1 were subjected to surface atomic ratio analysis and specific surface area analysis, and the results are shown in table 1; wherein, the surface atomic ratio analysis is carried out on Thermo ESCALAB 250, an Al Ka target (1486.6eV) is adopted as a light source, and C1 s-284.8 eV is adopted as an internal standard to correct the charge effect of the surface of the sample; specific surface area was measured on a Micromeritics ASAP 2020 instrument by N at 77K2Adsorption test and calculation by the Brunauer-Emmett-Teller (BET) method.
TABLE 1
As can be seen from Table 1, the Pt-based perovskite catalysts obtained in embodiments 1-12 of the present invention have a high surface Pt atomic ratio distribution, which is beneficial to improving the Pt utilization rate, thereby improving the electrochemical performance.
It can be seen from comparison between example 1 and examples 4 to 8 that, as the calcination temperature increases, the surface Pt content increases rapidly and then decreases slowly, and the specific surface area decreases gradually, which indicates that a higher calcination temperature is favorable for increasing the surface Pt content, but an excessively high temperature may cause a significant decrease in the specific surface area, but is unfavorable for increasing the catalytic activity, because the perovskite structure formed by low-temperature calcination is unstable, and the excessive dissolution causes Pt to agglomerate, so that the low-temperature calcination causes the surface Pt content to be lower, and the high-temperature calcination is favorable for increasing the crystallinity, thereby decreasing the specific surface area.
As can be seen from comparison between the example 1 and the examples 9 to 12, the surface Pt content also shows a trend of rising first and then falling along with the increase of the acid treatment time, and meanwhile, the acid treatment time can slightly increase the specific surface table, which shows that the longer acid treatment time is more beneficial to improving the surface Pt content and the specific surface area, so that the catalytic activity is improved, but the slight agglomeration is caused by the excessive acid treatment, so that the surface Pt content is reduced.
Comparative example 1, which was not acid treated, had a lower Pt content on the surface than example 1, probably because the absence of acid treatment did not favor more Pt exposed on the perovskite surface.
Test group 2
TEM tests were performed on the samples of examples 1, 4, 5, 12 and comparative example 1, and the results are shown in FIGS. 2 to 4. Among them, the TEM test was carried out in a transmission electron microscope (JEM-2100) of Japan Electron corporation (JEOL) at an electron acceleration voltage of 200 kV. The preparation method of the sample is as follows: and (3) taking a small amount of sample, ultrasonically dispersing the sample in absolute ethyl alcohol for 10min, taking 1-2 drops of liquid by using a dropper, dropwise adding the liquid on a carbon film, drying and testing.
As can be seen from the comparison of FIG. 2 and FIG. 3, after 90 minutes of acid treatment, the calcined LCP of 650 deg.C (example 4) and 850 deg.C (example 5) has different degrees of Pt agglomeration, which is probably due to the fact that the synthesized LCP has more defect sites on the surface at lower calcination temperature, so that the La and Co are excessively dissolved to collapse the surface structure, and further Pt agglomeration occurs; compared with the LCP surface (figure 1) baked at 1000 ℃, the structure is more stable, and the Pt nano particles are uniformly distributed on the surface of the catalyst after the acid treatment.
As can be seen from FIGS. 2 and 4, the LCP-1000 (comparative example 1) sample calcined at 1000 ℃ has a small amount of Pt nanoparticles with the size of 2-3 nm on the surface, and after 90 minutes of acid treatment (example 1), the Pt nanoparticles are obviously increased, which shows that after high-temperature treatment, a part of Pt in the LCP-1000 sample is segregated to the surface of the catalyst, but most of Pt is still uniformly dispersed in the internal crystal lattice of the perovskite and cannot be fully utilized, and after acid treatment, the segregation degree of Pt to the surface is obviously increased, so that the utilization rate of Pt is improved. When the acid treatment time was extended to 120min (example 12), slight agglomeration of Pt on the catalyst surface resulted.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. A preparation method of a Pt-based perovskite catalyst is characterized by comprising the following steps:
dispersing Pt source and soluble salt containing A, B element in water, adding complexing agent, mixing and stirring, drying and high-temperature roasting to obtain ABxPt(1-x)O3A perovskite;
the AB isxPt(1-x)O3And carrying out acid treatment and reduction on the perovskite to obtain the Pt-based perovskite catalyst.
2. The method according to claim 1, wherein the element a is at least one of lanthanum, praseodymium, and cerium, and the element B is at least one of cobalt, manganese, and aluminum.
3. The method for preparing a Pt-based perovskite-type catalyst according to claim 2, wherein the soluble salt used for the element a is a nitrate, chloride or acetate containing at least one of lanthanum, praseodymium and cerium, and the soluble salt used for the element B is a nitrate, chloride or acetate containing at least one of cobalt, manganese and aluminum; the Pt source is at least one of chloroplatinic acid and ammonium chloroplatinate.
4. The method for producing a Pt-based perovskite-type catalyst according to claim 1, wherein x is a molar ratio of a B element to a (B + Pt) element, and is in a range of 0.7 to 0.95.
5. The method for preparing a Pt-based perovskite catalyst according to claim 1, wherein the ratio of the total molar amount of the Pt source and the soluble salt containing A, B element to the molar amount of the complexing agent is 1 (0.6-1.2).
6. The method for preparing a Pt-based perovskite catalyst according to claim 1, wherein the high-temperature calcination temperature is 650 to 1300 ℃ and the high-temperature calcination time is 3 to 5 hours.
7. The preparation method of the Pt-based perovskite catalyst according to claim 1, wherein the acid selected in the acid treatment process is hydrochloric acid or nitric acid, the molar concentration is 3-6 mol/L, and the acid treatment time is 15-120 min.
8. The method for producing a Pt-based perovskite catalyst according to claim 7, wherein the acid treatment time is 60 to 120 min.
9. The preparation method of the Pt-based perovskite catalyst according to claim 1, wherein in the reduction process, the selected atmosphere is a mixture of nitrogen and hydrogen, the reduction temperature is 120-180 ℃, and the reduction time is 20-40 min.
10. The Pt-based perovskite catalyst according to any one of claims 1 to 9, which is obtained by the method for producing the Pt-based perovskite catalyst according to any one of claims 1 to 9.
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