FR3002464A1 - PROCESS FOR THE SYNTHESIS OF BIMETALLIC CATALYST PARTICLES BASED ON PLATINUM AND ANOTHER METAL AND METHOD FOR THE ELECTROCHEMICAL PRODUCTION OF HYDROGEN USING THE SYNTHESIS METHOD - Google Patents
PROCESS FOR THE SYNTHESIS OF BIMETALLIC CATALYST PARTICLES BASED ON PLATINUM AND ANOTHER METAL AND METHOD FOR THE ELECTROCHEMICAL PRODUCTION OF HYDROGEN USING THE SYNTHESIS METHOD Download PDFInfo
- Publication number
- FR3002464A1 FR3002464A1 FR1351679A FR1351679A FR3002464A1 FR 3002464 A1 FR3002464 A1 FR 3002464A1 FR 1351679 A FR1351679 A FR 1351679A FR 1351679 A FR1351679 A FR 1351679A FR 3002464 A1 FR3002464 A1 FR 3002464A1
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- metal
- platinum
- catalyst particles
- bimetallic catalyst
- salt
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 239000002245 particle Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 24
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 21
- 239000001257 hydrogen Substances 0.000 title claims abstract description 21
- 230000008569 process Effects 0.000 title claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 19
- 238000001308 synthesis method Methods 0.000 title description 2
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 238000006722 reduction reaction Methods 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 230000008014 freezing Effects 0.000 claims abstract description 7
- 238000007710 freezing Methods 0.000 claims abstract description 7
- 239000008246 gaseous mixture Substances 0.000 claims abstract description 6
- 238000001833 catalytic reforming Methods 0.000 claims abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010792 warming Methods 0.000 claims abstract description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 14
- 235000019253 formic acid Nutrition 0.000 claims description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 9
- 230000012010 growth Effects 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 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
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 4
- 238000010438 heat treatment Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000006056 electrooxidation reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229910018941 Pt3Sn Inorganic materials 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 230000035784 germination Effects 0.000 description 4
- 231100000572 poisoning Toxicity 0.000 description 4
- 230000000607 poisoning effect Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003698 anagen phase Effects 0.000 description 3
- 229910001092 metal group alloy Inorganic materials 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 244000052616 bacterial pathogen Species 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910020437 K2PtCl6 Inorganic materials 0.000 description 1
- 229910003178 Mo2C Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- ZMCCBULBRKMZTH-UHFFFAOYSA-N molybdenum platinum Chemical compound [Mo].[Pt] ZMCCBULBRKMZTH-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- FHMDYDAXYDRBGZ-UHFFFAOYSA-N platinum tin Chemical compound [Sn].[Pt] FHMDYDAXYDRBGZ-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
Classifications
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/345—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of ultraviolet wave energy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0238—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a carbon dioxide reforming step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Optics & Photonics (AREA)
- Electromagnetism (AREA)
- Toxicology (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Inert Electrodes (AREA)
Abstract
L'invention a pour objet un procédé de synthèse de particules de catalyseur bimétallique à base de platine et d'au moins un second métal caractérisé en ce qu'il comprend la réduction chimique d'un premier sel ou complexe à base de platine et d'au moins un second sel ou complexe à base dudit second métal, ladite réduction chimique comportant les étapes suivantes : - la réalisation d'un mélange comprenant ledit premier sel ou complexe à base de platine et ledit second sel ou complexe à base dudit second métal en présence d'un agent réducteur liquide ; - la mise en température comprise entre environ la température de congélation de l'eau et la température de congélation de l'agent réducteur, dudit mélange. L'invention a aussi pour objet une méthode de production d'hydrogène caractérisé en ce qu'elle comprend une réaction de réformage catalytique en présence de particules de catalyseur obtenu selon l'invention et d'un mélange gazeux comprenant des composés hydrocarbonés.The subject of the invention is a process for the synthesis of particles of bimetallic catalyst based on platinum and at least one second metal, characterized in that it comprises the chemical reduction of a first salt or complex based on platinum and platinum. at least one second salt or complex based on said second metal, said chemical reduction comprising the following steps: the production of a mixture comprising said first salt or platinum-based complex and said second salt or complex based on said second metal in the presence of a liquid reducing agent; - Warming up between about the freezing temperature of the water and the freezing temperature of the reducing agent, said mixture. The invention also relates to a method for producing hydrogen, characterized in that it comprises a catalytic reforming reaction in the presence of catalyst particles obtained according to the invention and a gaseous mixture comprising hydrocarbon compounds.
Description
Procédé de synthèse de particules de catalyseur bimétallique à base de platine et d'un autre métal et méthode de production électrochimique d'hydrogène utilisant ledit procédé de synthèse Le domaine de l'invention est celui des piles à combustible H2/02. L'utilisation de ce type de pile à combustible dans l'industrie automobile en lieu et place des moteurs à combustion interne rencontre toujours des problèmes liés au stockage de l'hydrogène : les réservoirs d'hydrogène sous pression (stockage gazeux) sont potentiellement dangereux et les hydrures métalliques (stockage sous forme solide) sont inappropriés en raison de leur densité énergétique faible comme décrit dans l'article de : Schlapbach L. Züttel A. Hydrogen-storage materials for mobile applications. Nature 2001 ; 414 :353-8.The field of the invention is that of H2 / 02 fuel cells. A process for the synthesis of platinum-metal and other metal-based bimetallic catalyst particles and method for the electrochemical production of hydrogen using said synthesis process. The use of this type of fuel cell in the automotive industry in place of internal combustion engines still faces problems related to the storage of hydrogen: pressurized hydrogen tanks (gas storage) are potentially dangerous and metal hydrides (storage in solid form) are unsuitable because of their low energy density as described in the article by: Schlapbach L. Züttel A. Hydrogen-storage materials for mobile applications. Nature 2001; 414: 353-8.
La production d'hydrogène à bord du véhicule par reformage catalytique offre une solution alternative au stockage direct d'hydrogène comme décrit dans l'article de : Basile A, Galluci F, Paturzo L. « Hydrogen production from methanol by oxidative steam reforming carried out in a membrane reactor », Catalysis today 2005 ; 104:251-9, mais une étape de purification est nécessaire pour alimenter la pile à combustible. Pour ce type d'application, les biocarburants et des hydrocarbures gazeux comme le gaz naturel ou liquides tels que l'alcool, l'essence ou le gasoil sont potentiellement des sources d'hydrogène et une cellule électrochimique connectée à une alimentation électrique de faible puissance peut être utilisée pour extraire à basse température l'hydrogène du mélange gazeux contenant le monoxyde de carbone (CO), dioxyde de carbone (CO2), méthane (CH4) et d'autres gaz. En appliquant une tension électrique suffisante aux bornes de la cellule, l'électro-oxydation de l'hydrogène et du monoxyde de carbone ont 30 lieu à l'anode : H2 -> 2H+ + 2e- (E°(H+/H2)=0 vs. ESH, potentiel standard d'équilibre électrochimique, ESH étant le potentiel de l'électrode standard à hydrogène) COads + H2O CO2 + 2H+ + 2e- 35 comme décrit dans l'article de : M. Ciureanu et al., "Electrochemical Impedance Study of Electrode-Membrane Assemblies in PEM Fuel Cells I.The production of hydrogen on board the vehicle by catalytic reforming offers an alternative solution to the direct storage of hydrogen as described in the article by: Basil A, Galluci F, Paturzo L. "Hydrogen production from methanol by oxidative steam reforming carried out in a membrane reactor ", Catalysis today 2005; 104: 251-9, but a purification step is required to feed the fuel cell. For this type of application, biofuels and gaseous hydrocarbons such as natural gas or liquids such as alcohol, gasoline or gas oil are potentially sources of hydrogen and an electrochemical cell connected to a low-power power supply. can be used to extract hydrogen at low temperature from the gaseous mixture containing carbon monoxide (CO), carbon dioxide (CO2), methane (CH4) and other gases. By applying a sufficient electrical voltage across the cell, the electro-oxidation of hydrogen and carbon monoxide takes place at the anode: H2 -> 2H + + 2e- (E ° (H + / H2) = 0 vs. ESH, standard electrochemical equilibrium potential, ESH being the potential of the standard hydrogen electrode) COads + H2O CO2 + 2H + + 2e-35 as described in the article by: M. Ciureanu et al., " Electrochemical Impedance Study of Membrane Electrode Assemblies in PEM Fuel Cells I.
Electro-oxidation of H2 and H2/CO Mixtures on Pt-Based Gas-Diffusion Electrodes" Journal of the Electrochemical Society 1999, 146, 4031-4040. Le platine est très souvent utilisé en tant que catalyseur de réaction, dans les systèmes électrochimiques, mais son utilisation pour une 5 application de purification comme matériau d'anode pose problème bien qu'il soit le meilleur matériau utilisé à basse température pour la réaction d'électro-oxydation d'hydrogène (H2 2H+ + 2e-). En effet, le platine (Pt) est onéreux, rare et moins performant à bas potentiel à cause de la facilité qu'a le monoxyde de carbone (contenu 10 dans l'hydrogène reformé) à l'empoisonner. Cet empoisonnement se fait par adsorption du CO à la surface du Pt de façon irréversible en bloquant les sites d'adsorption disponibles, empêchant ainsi l'adsorption de l'hydrogène, et son oxydation. Or, l'électro-oxydation du CO à la surface du Pt supporté sur du 15 carbone, c'est-à-dire du CO en CO2 (CO + H2O CO2 + 2H+ + 2e-) se fait à des potentiels relativement élevés se situant autour de 0,7 à 0,8 V vs. ESH, ce qui nécessite un apport d'énergie non négligeable. Pour pallier aux difficultés rencontrées avec le platine Pt liées essentiellement à sa mauvaise tolérance au monoxyde de carbone CO, de 20 nouveaux catalyseurs d'anode sont recherchés. Pour aboutir à ces nouveaux types de catalyseurs, l'élaboration d'un alliage de Pt avec un métal de transition peut être envisagée ou l'association du Pt fortement divisé à une phase du type oxyde métallique. Plusieurs alliages de platine tels que le platine-ruthénium (Pt-Ru), le platine- 25 étain (Pt-Sn), le platine-molybdène (Pt-Mo), le platine-cobalt (Pt-Co) supportés sur du noir de carbone de grande surface spécifique font l'objet d'études dans le but de trouver le meilleur alliage à base de platine qui possède une bonne tolérance au monoxyde de carbone CO et qui permette d'autre part d'oxyder ledit monoxyde de carbone CO à bas potentiel. 30 II est par ailleurs connu que les performances de ces catalyseurs anodiques vis-à-vis de l'électro-oxydation de H2/CO dépendent de leur structure, de leur composition chimique, de la taille nanométrique des particules et de la nature de leur support. La maîtrise de la technique d'élaboration et de la méthode de préparation des catalyseurs permet de 35 contrôler les propriétés physico-chimiques. Les nanoparticules métalliques sont généralement synthétisées par réduction chimique de sels ou complexes métalliques en présence d'un agent réducteur. Lors de la synthèse, le mécanisme de développement des nanoparticules se fait par germination et croissance. Cette étape est importante car elle détermine la taille des particules et impacte par conséquent, la surface électroactive du catalyseur. L'obtention des nanoparticules de catalyseur par réduction chimique de sels ou complexes métalliques en présence d'un agent réducteur est une méthode simple à mettre en oeuvre mais la maitrise et le contrôle des phases de germination et croissance des nanoparticules restent un enjeu majeur. C'est pourquoi et dans ce contexte, la présente invention, a pour objet une méthode basée sur l'optimisation des conditions opératoires de synthèse afin de limiter la phase de croissance des nanoparticules et 15 favoriser celle de la germination permettant d'accroître le nombre de germes. En comparaison avec une évolution spontanée lors de la synthèse de particules par réduction chimique (sans modification des paramètres opératoires), la limitation de la phase de croissance permet d'obtenir des nanoparticules de petites tailles typiquement de l'ordre de 2 à 5 nm et un 20 nombre de particules plus important. La conjugaison de ces deux aspects offre une configuration microstructurale dans laquelle la surface électroactive du catalyseur est optimale. La modification de la température à laquelle la réduction chimique 25 des sels et complexes métalliques a lieu, représente le moyen le plus efficace pour réduire la vitesse de croissance des particules car les deux paramètres évoluent dans le même sens. Plus précisément, la présente invention a pour objet un procédé de synthèse de particules de catalyseur bimétallique à base de platine et 30 d'au moins un second métal caractérisé en ce qu'il comprend la réduction chimique d'un premier sel ou complexe à base de platine et d'au moins un second sel ou complexe à base dudit second métal, ladite réduction chimique comportant les étapes suivantes : - la réalisation d'un mélange comprenant ledit premier sel ou 35 complexe à base de platine et ledit second sel ou complexe à base dudit second métal, en présence d'un agent réducteur liquide ; - la mise en température comprise entre environ la température de congélation de l'eau et la température de congélation de l'agent réducteur, dudit mélange. Selon une variante de l'invention, l'agent réducteur est l'acide formique, la température de ladite réduction chimique étant effectuée à une température comprise entre environ 0°C et 8°C, pouvant avantageusement être de l'ordre de 4°C.Electro-Oxidation of H2 and H2 / CO Mixtures on Pt-Based Gas-Diffusion Electrodes "Journal of the Electrochemical Society 1999, 146, 4031-4040 Platinum is very often used as a reaction catalyst in electrochemical systems, but its use for a purification application as anode material is problematic although it is the best material used at low temperature for the hydrogen electro-oxidation reaction (H2 2H + + 2e-). platinum (Pt) is expensive, rare and less powerful at low potential because of the ease of carbon monoxide (contained in reformed hydrogen) in poisoning, poisoning by adsorption of CO to the surface of the Pt irreversibly by blocking the available adsorption sites, thus preventing the adsorption of hydrogen, and its oxidation, whereas the electro-oxidation of CO on the surface of the carbon supported Pt, that is CO2 in CO (CO + H2O CO2 + 2H + + 2e-) is at relatively high potentials ranging from 0.7 to 0.8 V vs. ESH, which requires a significant supply of energy. To overcome the difficulties encountered with platinum Pt mainly related to its poor tolerance to carbon monoxide CO, 20 new anode catalysts are sought. To achieve these new types of catalysts, the development of a Pt alloy with a transition metal can be envisaged or the combination of highly divided Pt with a metal oxide phase. Several platinum alloys such as platinum-ruthenium (Pt-Ru), platinum-tin (Pt-Sn), platinum-molybdenum (Pt-Mo), platinum-cobalt (Pt-Co) supported on black of high surface area carbon are studied in order to find the best platinum-based alloy that has a good tolerance to carbon monoxide CO and that also allows to oxidize said carbon monoxide CO low potential. It is moreover known that the performance of these anodic catalysts with respect to the electro-oxidation of H 2 / CO depends on their structure, their chemical composition, the nanometric size of the particles and the nature of their composition. support. The mastery of the preparation technique and the catalyst preparation method makes it possible to control the physicochemical properties. The metal nanoparticles are generally synthesized by chemical reduction of salts or metal complexes in the presence of a reducing agent. During the synthesis, the mechanism of development of the nanoparticles is by germination and growth. This step is important because it determines the particle size and therefore impacts the electroactive surface of the catalyst. Obtaining the catalyst nanoparticles by chemical reduction of salts or metal complexes in the presence of a reducing agent is a simple method to implement but the control and control of the germination and growth phases of the nanoparticles remain a major issue. Therefore, and in this context, the subject of the present invention is a method based on the optimization of the operating conditions of synthesis in order to limit the growth phase of the nanoparticles and to favor that of the germination making it possible to increase the number of germs. In comparison with a spontaneous evolution during the synthesis of particles by chemical reduction (without modification of the operating parameters), the limitation of the growth phase makes it possible to obtain nanoparticles of small sizes, typically of the order of 2 to 5 nm and a larger number of particles. The combination of these two aspects provides a microstructural configuration in which the electroactive surface of the catalyst is optimal. The modification of the temperature at which the chemical reduction of the metal salts and complexes takes place represents the most effective way to reduce the growth rate of the particles as the two parameters evolve in the same direction. More specifically, the subject of the present invention is a process for the synthesis of platinum-based bimetallic catalyst particles and of at least one second metal, characterized in that it comprises the chemical reduction of a first salt or complex based on platinum and at least a second salt or complex based on said second metal, said chemical reduction comprising the following steps: - the production of a mixture comprising said first salt or platinum complex and said second salt or complex based on said second metal, in the presence of a liquid reducing agent; - Warming up between about the freezing temperature of the water and the freezing temperature of the reducing agent, said mixture. According to a variant of the invention, the reducing agent is formic acid, the temperature of said chemical reduction being carried out at a temperature of between approximately 0 ° C. and 8 ° C., advantageously being of the order of 4 ° C. vs.
Selon une variante de l'invention, l'agent réducteur est l'hydrazine, la température de ladite réduction étant effectuée à une température comprise entre 0°C et 2°C. Selon une variante de l'invention, l'agent réducteur est le formaldéhyde, la température de ladite réduction étant effectuée à une 15 température comprise entre -19°C et 0°C. Selon une variante de l'invention, le procédé comprend le mélange de sel ou de complexe de platine et de sel ou de complexe dudit second métal, en présence de particules de noir de carbone ou d'oxyde métallique ou de nitrure métallique ou de carbure métallique. 20 Selon une variante de l'invention, la quantité d'agent réducteur est supérieure ou égale à la quantité nécessaire pour procéder à la réduction chimique de l'ensemble des sels ou complexes du platine et de ceux du second métal. Selon une variante de l'invention, la réaction est effectuée en 25 présence d'une source d'énergie additionnelle permettant d'accélérer l'opération de réduction chimique sans favoriser la croissance de nanoparticules. Selon une variante de l'invention, la source d'énergie additionnelle est une source de rayonnements ultra-violets. 30 Selon une variante de l'invention, la source de rayonnements ultra-violets émet dans une gamme de longueurs d'onde comprises entre environ 200 nm et 300 nm. Selon une variante de l'invention, le second métal est de l'étain, ou du ruthénium, ou du molybdène, ou du cobalt.According to a variant of the invention, the reducing agent is hydrazine, the temperature of said reduction being carried out at a temperature between 0 ° C. and 2 ° C. According to a variant of the invention, the reducing agent is formaldehyde, the temperature of said reduction being carried out at a temperature of between -19 ° C. and 0 ° C. According to a variant of the invention, the process comprises the mixture of salt or platinum complex and salt or complex of said second metal, in the presence of particles of carbon black or metal oxide or metal nitride or carbide metallic. According to a variant of the invention, the amount of reducing agent is greater than or equal to the amount necessary to carry out the chemical reduction of all the platinum salts and complexes and those of the second metal. According to a variant of the invention, the reaction is carried out in the presence of an additional energy source making it possible to accelerate the chemical reduction operation without promoting the growth of nanoparticles. According to a variant of the invention, the additional energy source is a source of ultraviolet radiation. According to a variant of the invention, the source of ultraviolet radiation emits in a wavelength range of between about 200 nm and 300 nm. According to a variant of the invention, the second metal is tin, or ruthenium, or molybdenum, or cobalt.
L'invention a aussi pour objet une méthode de production électrochimique d'hydrogène caractérisé en ce qu'elle comprend une réaction de reformage catalytique en présence de particules de catalyseur obtenu selon l'invention et d'un mélange gazeux comprenant des composés hydrocarbonés. Selon une variante de l'invention, le mélange gazeux comprend du monoxyde de carbone, du dioxyde de carbone et du méthane. L'invention sera mieux comprise et d'autres avantages 10 apparaîtront à la lecture de la description qui va suivre donnée à titre non limitatif et grâce aux figures annexées parmi lesquelles : - la figure 1 illustre les spectres d'absorption UV des ions PtC162-; - la figure 2 illustre la distribution de la taille de particules des catalyseurs Pt3Sn/C synthétisés à température ambiante et à 15 4°C, selon le procédé de l'invention ; - la figure 3 illustre les voltampérogrammes cycliques obtenus sur Pt3Sn/C synthétisés à température ambiante et à 4°C dans une solution de H2504 de concentration 0,5 M à 25°C ; - la figure 4 illustre l'évolution du courant d'électro-oxydation de 20 H2 sur Pt3Sn/C synthétisés à température ambiante et à 4°C dans une solution de H2SO4 de concentration 0,5 M après avoir soumis le catalyseur à un mélange de gaz composé de 50 ppm de CO dans H2 et à 0,24 V vs. ERH et atteint un état quasi stationnaire de l'évolution du courant d'oxydation de 25 l'hydrogène au cours du temps. Pour la synthèse d'un catalyseur d'alliage platine-métal (Pt-M), le Demandeur utilise la méthode FAM (Formic Acid Method) telle que décrite dans l'article E.I. Santiago et al. « CO tolerance on PtMo/C electrocatalysts 30 prepared by the formic acid Method » Electrochimica Acta 48 (2003) 35273534. Selon la présente invention, il est proposé d'utiliser des solutions de sels ou complexes de Pt et d'un allié métallique comme précurseurs de catalyseurs Pt-M supportés ou non sur du noir de carbone de grande surface 35 spécifique, un oxyde métallique (TiO2, ZrO2, A1203,...) ou des nitrures métalliques (TiN, TaN, BN), des carbures métalliques (TiC, WC, W2C, Mo2C,- - -)- Dans le cas d'un support de carbone, les solutions de sels ou complexes de Pt et de l'élément métallique allié M sont mélangés au support de carbone et l'ensemble est agité vigoureusement aux ultra-sons pendant au moins une demi-heure, temps nécessaire pour obtenir un mélange homogène. Le volume des solutions est déterminé à partir de la concentration des solutions et de manière à obtenir la composition atomique de l'alliage métallique souhaitée. La masse de support de nanoparticules métalliques utile pour la synthèse est déterminée de façon à ce qu'elle représente 50% de la masse du catalyseur synthétisé. L'acide formique est utilisé comme agent réducteur et est rajouté au mélange précédemment décrit. Le volume de l'acide formique doit être en excès pour que la 15 réduction chimique des sels ou complexes métalliques soit achevée. L'ensemble du mélange est par la suite porté à une température comprise entre la température de congélation de l'eau et celle de l'acide formique. Au bout de 12 à 72 heures, la réduction chimique est achevée et on obtient une poudre métallique représentant le catalyseur. 20 L'abaissement de la température favorise la diminution de la vitesse de croissance des nanoparticules et allonge par conséquent la durée de réduction chimique des sels métalliques. Pour pallier cet allongement de durée, il convient d'accélérer la réaction de réduction chimique sans pour autant augmenter la vitesse de croissance. 25 Le flacon contenant le mélange peut avantageusement être exposé à une source d'énergie par exemple de rayons ultraviolets (UV) qui permettent grâce à cet apport d'énergie d'accélérer la réaction (la germination des particules), favorisant ainsi la multiplicité de germes à l'état nanoparticulaire sans pour autant favoriser leur croissance. La longueur 30 d'onde des rayons UV est choisie de préférence entre 200 et 300 nm, correspondant à la zone d'absorption du platine complexe de Pt, comme montré sur la figure 1. 35 Exemple de réalisation : Des catalyseurs de Pt-Sn/C de composition molaire 3 :1 ont été synthétisés par réduction chimique à l'acide formique.The invention also relates to an electrochemical hydrogen production method characterized in that it comprises a catalytic reforming reaction in the presence of catalyst particles obtained according to the invention and a gaseous mixture comprising hydrocarbon compounds. According to a variant of the invention, the gaseous mixture comprises carbon monoxide, carbon dioxide and methane. The invention will be better understood and other advantages will become apparent on reading the following description, which is given in a nonlimiting manner and by virtue of the appended figures in which: FIG. 1 illustrates the UV absorption spectra of PtC162-ions; ; FIG. 2 illustrates the particle size distribution of the Pt3Sn / C catalysts synthesized at room temperature and at 4 ° C., according to the process of the invention; FIG. 3 illustrates the cyclic voltammograms obtained on Pt3Sn / C synthesized at room temperature and at 4 ° C. in a solution of H2504 of concentration 0.5 M at 25 ° C .; FIG. 4 illustrates the evolution of the electro-oxidation current of 20 H 2 on Pt 3 Sn / C synthesized at room temperature and at 4 ° C. in a 0.5 M solution of H2SO4 after having subjected the catalyst to a mixture of gas composed of 50 ppm CO in H2 and 0.24 V vs. ERH and reaches an almost stationary state of evolution of the oxidation current of hydrogen over time. For the synthesis of a platinum-metal alloy (Pt-M) catalyst, the Applicant uses the FAM (Formic Acid Method) method as described in the article E.I. Santiago et al. According to the present invention, it is proposed to use solutions of salts or complexes of Pt and of a metallic alloy, for example, as described in US Pat. No. 4,151,372. precursors of Pt-M catalysts supported or not on high surface area carbon black, a metal oxide (TiO 2, ZrO 2, Al 2 O 3,...) or metal nitrides (TiN, TaN, BN), metal carbides ( TiC, WC, W2C, Mo2C, - - -) - In the case of a carbon support, the solutions of salts or complexes of Pt and of the alloy metal element M are mixed with the carbon support and the assembly is shaken vigorously with ultrasound for at least half an hour, the time required to obtain a homogeneous mixture. The volume of the solutions is determined from the concentration of the solutions and so as to obtain the atomic composition of the desired metal alloy. The support mass of metal nanoparticles useful for the synthesis is determined so that it represents 50% of the mass of the synthesized catalyst. Formic acid is used as a reducing agent and is added to the previously described mixture. The volume of the formic acid must be in excess so that the chemical reduction of the metal salts or complexes is completed. The whole mixture is then brought to a temperature between the freezing temperature of water and that of formic acid. After 12 to 72 hours, the chemical reduction is complete and a metal powder is obtained representing the catalyst. The lowering of the temperature favors the decrease of the growth rate of the nanoparticles and consequently extends the duration of chemical reduction of the metal salts. To overcome this lengthening of time, it is necessary to accelerate the chemical reduction reaction without increasing the growth rate. The vial containing the mixture may advantageously be exposed to a source of energy, for example ultraviolet (UV) rays which make it possible, by virtue of this supply of energy, to accelerate the reaction (the germination of the particles), thus favoring the multiplicity of germs in the nanoparticular state without promoting their growth. The wavelength of the UV rays is preferably chosen between 200 and 300 nm, corresponding to the absorption zone of the complex platinum of Pt, as shown in FIG. 1. Exemplary embodiment: Pt-Sn catalysts / C of 3: 1 molar composition were synthesized by chemical reduction with formic acid.
Les solutions de K2PtC16, 6H20 et SnCl2, 2H20 de chez Sigma- Aldrich ont été utilisées comme précurseurs des catalyseurs de Pt-Sn supportés sur du noir de carbone de grande surface spécifique (Vulcan XC72R, Cabot Corp., 250 m2/g). Les solutions aqueuses de sels de platine et d'étain de concentration 0,01M ont été mélangées en présence du noir de carbone et agitées vigoureusement aux ultra-sons pendant une durée d'environ une heure. Les volumes des solutions K2PtC16, 6H20 et SnCl2, 2H20 mélangées sont respectivement de 15 ml et 5 ml de façon à obtenir un rapport atomique de 3 : 1.The solutions of K2PtC16, 6H20 and SnCl2, 2H20 from Sigma-Aldrich were used as precursors of Pt-Sn catalysts supported on high surface area carbon black (Vulcan XC72R, Cabot Corp., 250 m 2 / g). Aqueous solutions of platinum and tin salts of 0.01M concentration were mixed in the presence of carbon black and vigorously shaken with ultrasound for a period of about one hour. The volumes of the mixed K2PtCl6, 6H20 and SnCl2, 2H20 solutions are respectively 15 ml and 5 ml so as to obtain an atomic ratio of 3: 1.
Une grande quantité d'acide formique HCOOH (ACS reagent, supérieure ou égale à 98% Sigma-Aldrich) d'un rapport molaire de l'ordre de 1000: 1, entre l'acide formique et les sels métalliques, utilisé comme agent réducteur, est ajoutée au mélange pour permettre une réduction simultanée des sels de platine et d'étain.A large amount of formic acid HCOOH (ACS reagent, greater than or equal to 98% Sigma-Aldrich) with a molar ratio of the order of 1000: 1, between formic acid and metal salts, used as a reducing agent is added to the mixture to allow a simultaneous reduction of the platinum and tin salts.
Deux exemples de conditions opératoires de synthèse ont été réalisés : - un premier exemple à température ambiante pendant 24 heures ; - un second exemple à 4°C pendant 72 heures. Au bout de la durée précisée précédemment, une poudre métallique a été obtenue. La masse de Pt+Sn représente 50% en masse du catalyseur. La température de 4°C a été choisie de manière à ce qu'elle soit comprise entre 0 et 8°C. L'objectif de réaliser la synthèse à cette température est de 30 réduire lors de la synthèse, la vitesse de croissance des nanoparticules qui a une dépendance croissance avec la température. Les résultats obtenus sont répertoriés dans le Tableau ci-après et concernent les propriétés physico-chimiques des catalyseurs de Pt3Sn/C 35 synthétisés à température ambiante et à 4°C.Two examples of synthetic operating conditions were carried out: a first example at room temperature for 24 hours; a second example at 4 ° C. for 72 hours. At the end of the period specified above, a metal powder was obtained. The mass of Pt + Sn represents 50% by weight of the catalyst. The temperature of 4 ° C was chosen so that it was between 0 and 8 ° C. The objective of carrying out the synthesis at this temperature is to reduce during the synthesis, the growth rate of the nanoparticles which has a growth dependence with temperature. The results obtained are listed in the table below and relate to the physicochemical properties of the Pt3Sn / C35 catalysts synthesized at ambient temperature and at 4 ° C.
Catalyseur Taille moyenne Surface Potentiel d'électrooxydation du CO en V (volts) des particules électroactive (Hupd) cm2 Pt cm- nm 2 qeo Pt3Sn/C 7,5 266 0,38 (Température ambiante) Pt3Sn/C à 4°C 5 379 0,28 La surface électro-active correspond plus précisément à la surface électro-chimiquement active pour les réactions considérées, que l'on cherche à augmenter. La figure 2 illustre les distributions de taille de particules de 10 catalyseurs Pt3Sn/C synthétisées à température ambiante et à 4°C qui met en évidence le pourcentage élevé de particules de faible taille, typiquement de 3 à 4 nm, avec le procédé de synthèse de l'invention. Le Demandeur a réalisé les voltampérogrammes cycliques en demi cellule électrochimique à 25°C avec une vitesse de balayage de 10 15 mV/s, relatifs aux différents catalyseurs comme illustré en figure 3, plus précisément obtenus sur Pt3Sn/C synthétisés à température ambiante et à 4°C après avoir soumis le catalyseur à un mélange de gaz composé de 50 ppm de CO dans H2 et à 0,24 V vs. ERH et atteint un état quasi stationnaire de l'évolution du courant d'oxydation de l'hydrogène au cours du temps 20 (courbe 3c : catalyseur synthétisé à 25°C, courbe 3b : catalyseur synthétisé à 4°C). Ces courbes peuvent être comparées à celle obtenue sur le catalyseur non soumis au gaz polluant (courbe 3a). Dans le cas du catalyseur synthétisé à 25°C (courbe 3c), la pollution par le CO est quasi 25 totale, aucun pic de désorption des espèces H - adsorbées n'est visible entre 0 et 0,4 V vs. ERH. Un important pic d'électro-oxydation du CO est cependant nettement visible entre 0,4 et 1 V vs. ERH. Pour le catalyseur synthétisé à 4°C (courbe 3b), les pics de désorption des espèces H adsorbées ne sont quasiment pas réduits par rapport à l'échantillon n'ayant pas été pollué (courbe 3a). Il faut toutefois noter la présence d'un faible courant d'oxydation du CO, apparaissant dès 0,28 V vs. ERH et s'étalant jusqu'à 0,9 V vs. ERH. Il est rappelé que la voltamétrie est une méthode d'électro-analyse basée sur la mesure du flux de courant résultant de la réduction ou de l'oxydation des composés qui entrent en contact avec une électrode de travail (l'échantillon étudié) sous l'effet d'une variation contrôlée de la différence de potentiel avec une électrode au potentiel fixe, appelée électrode de référence. Elle permet d'identifier et de mesurer quantitativement un grand nombre de composés et également d'étudier les réactions chimiques incluant ces composés.Catalyst Medium Size Surface Potential for electrooxidation of CO at V (volts) electroactive particles (Hupd) cm2 Pt cm-nm 2 qe Pt3Sn / C 7.5 266 0.38 (Ambient temperature) Pt3Sn / C at 4 ° C 5 379 0.28 The electro-active surface corresponds more precisely to the electro-chemically active surface for the reactions considered, which one seeks to increase. Figure 2 illustrates the particle size distributions of Pt3Sn / C catalysts synthesized at room temperature and at 4 ° C which demonstrates the high percentage of small particles, typically 3 to 4 nm, with the synthesis method. of the invention. The Applicant has carried out the cyclic voltammograms in a half electrochemical cell at 25 ° C. with a scanning speed of 10 15 mV / s, relative to the various catalysts as illustrated in FIG. 3, more precisely obtained on Pt3Sn / C synthesized at room temperature and at room temperature. 4 ° C after subjecting the catalyst to a gas mixture composed of 50 ppm CO in H2 and 0.24 V. ERH and reached a quasi stationary state of evolution of the oxidation current of hydrogen over time (curve 3c: catalyst synthesized at 25 ° C, curve 3b: catalyst synthesized at 4 ° C). These curves can be compared with that obtained on the catalyst not subjected to the pollutant gas (curve 3a). In the case of the catalyst synthesized at 25 ° C. (curve 3c), the pollution with CO is almost complete, no desorption peak of the adsorbed H species is visible between 0 and 0.4 V. ERH. A significant peak of electro-oxidation of CO is however clearly visible between 0.4 and 1 V vs. ERH. For the catalyst synthesized at 4 ° C. (curve 3b), the desorption peaks of the adsorbed H species are practically not reduced compared with the sample that has not been polluted (curve 3a). It should be noted, however, the presence of a low oxidation current of CO, appearing as of 0.28 V vs. ERH and spreading to 0.9 V vs. ERH. It is recalled that voltammetry is an electro-analysis method based on the measurement of the current flow resulting from the reduction or oxidation of the compounds which come into contact with a working electrode (the sample studied) under effect of a controlled variation of the potential difference with a fixed potential electrode, called the reference electrode. It makes it possible to identify and quantitatively measure a large number of compounds and also to study the chemical reactions including these compounds.
Le fort pouvoir d'absorption peut être caractérisé par l'absence de pics d'oxydation (courant positifs) sur le voltammogramme présentant la densité de courant mesuré en fonction du potentiel appliqué E à l'électrode de travail. L'absence de ces pics sur le voltammogramme traduit le blocage des sites d'adsorption du catalyseur par une autre espèce.The high absorption power can be characterized by the absence of oxidation peaks (positive current) on the voltammogram having the current density measured as a function of the applied potential E to the working electrode. The absence of these peaks on the voltammogram indicates the blocking of the adsorption sites of the catalyst by another species.
Le Demandeur a également suivi l'évolution du courant d'électro- oxydation de H2 sur Pt3Sn/C synthétisés à température ambiante et à 4°C dans un dispositif de demi cellule électrochimique, lorsque l'électrode est alimentée par un mélange de gaz composé de 50 ppm de CO dans H2 et soumise à un potentiel de 0,24 V vs. ERH. La figure 4 montre via les courbes 4a et 4b la différence de comportement avec un catalyseur réalisé selon la présente invention à une température de 4°C, comparativement à un catalyseur réalisé à température ambiante. La densité de courant mesurée au cours du temps (j) est rapportée à celle mesurée lorsque l'échantillon est alimenté en hydrogène 30 pur (jmax). Initialement, le catalyseur n'est pas pollué donc j = jmax et j/jmax=1. Dans le cas du catalyseur synthétisé à 25°C (courbe 4a), la densité de courant mesurée au cours du temps diminue rapidement pour atteindre 71% du courant initial après 1 heure d'empoisonnement au CO. Pour le catalyseur synthétisé à 4°C, le courant mesuré après 1 heure d'empoisonnement est de 93% du courant initial. Le catalyseur synthétisé à 4°C est donc beaucoup plus tolérant au CO que celui synthétisé à 25°C.The Applicant has also followed the evolution of the electro-oxidation current of H2 on Pt3Sn / C synthesized at room temperature and at 4 ° C. in an electrochemical half-cell device, when the electrode is fed with a mixture of compound gases. 50 ppm CO in H2 and subject to a potential of 0.24 V vs. ERH. FIG. 4 shows via the curves 4a and 4b the difference in behavior with a catalyst produced according to the present invention at a temperature of 4 ° C., compared with a catalyst produced at ambient temperature. The current density measured over time (j) is related to that measured when the sample is supplied with pure hydrogen (jmax). Initially, the catalyst is not polluted so j = jmax and j / jmax = 1. In the case of the catalyst synthesized at 25 ° C (curve 4a), the current density measured over time decreases rapidly to 71% of the initial current after 1 hour of CO poisoning. For the catalyst synthesized at 4 ° C., the current measured after 1 hour of poisoning is 93% of the initial current. The catalyst synthesized at 4 ° C. is therefore much more tolerant to CO than that synthesized at 25 ° C.
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FR1351679A FR3002464A1 (en) | 2013-02-26 | 2013-02-26 | PROCESS FOR THE SYNTHESIS OF BIMETALLIC CATALYST PARTICLES BASED ON PLATINUM AND ANOTHER METAL AND METHOD FOR THE ELECTROCHEMICAL PRODUCTION OF HYDROGEN USING THE SYNTHESIS METHOD |
US14/767,267 US20160010229A1 (en) | 2013-02-26 | 2014-02-24 | Method for synthesizing bimetal catalyst particles made of platinum and of another metal and use thereof in an electrochemical hydrogen production method |
PCT/EP2014/053535 WO2014131724A1 (en) | 2013-02-26 | 2014-02-24 | Method for synthesizing bimetal catalyst particles made of platinum and of another metal and use thereof in an electrochemical hydrogen production method |
EP14706561.9A EP2961527A1 (en) | 2013-02-26 | 2014-02-24 | Method for synthesizing bimetal catalyst particles made of platinum and of another metal and use thereof in an electrochemical hydrogen production method |
JP2015558484A JP2016513013A (en) | 2013-02-26 | 2014-02-24 | Method for the synthesis of bimetallic catalyst particles made of platinum and another metal and its use in an electrochemical hydrogen production method |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0091165A1 (en) * | 1982-04-01 | 1983-10-12 | Nederlandse Organisatie Voor Zuiver-Wetenschappelijk Onderzoek (ZWO) | A silver catalyst and a method for the preparation thereof |
WO2005063390A1 (en) * | 2003-12-25 | 2005-07-14 | Nissan Motor Co., Ltd. | Powdery catalyst, exhaust-gas purifying catalyzer, and powdery catalyst production method |
-
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0091165A1 (en) * | 1982-04-01 | 1983-10-12 | Nederlandse Organisatie Voor Zuiver-Wetenschappelijk Onderzoek (ZWO) | A silver catalyst and a method for the preparation thereof |
WO2005063390A1 (en) * | 2003-12-25 | 2005-07-14 | Nissan Motor Co., Ltd. | Powdery catalyst, exhaust-gas purifying catalyzer, and powdery catalyst production method |
Non-Patent Citations (6)
Title |
---|
ALEXEI L N PINHEIRO ET AL: "Electrocatalysis on Noble Metal and Noble Metal Alloys Dispersed on High Surface Area Carbon", JOURNAL OF NEW MATERIALS FOR ELECTROCHEMICAL SYSTEMS J. NEW. MAT. ELECTROCHEM. SYSTEMS, 1 January 2003 (2003-01-01), pages 1 - 8, XP055085347, Retrieved from the Internet <URL:http://www.groupes.polymtl.ca/jnmes/archives/2003_01/v06n01a01_p001-008.pdf> * |
ANTOLINI E ET AL: "Carbon supported Pt-Cr alloys as oxygen-reduction catalysts for direct methanol fuel cells", JOURNAL OF APPLIED ELECTROCHEMISTRY, KLUWER ACADEMIC PUBLISHERS, DO, vol. 36, no. 3, 1 March 2006 (2006-03-01), pages 355 - 362, XP019247516, ISSN: 1572-8838, DOI: 10.1007/S10800-005-9072-0 * |
CASTRO LUNA A M ET AL: "Effect of thermal treatment on the performance of CO-tolerant anodes for polymer electrolyte fuel cells", ELECTROCHEMISTRY COMMUNICATIONS, ELSEVIER, AMSTERDAM, NL, vol. 2, no. 4, 1 April 2000 (2000-04-01), pages 222 - 225, XP027407420, ISSN: 1388-2481, [retrieved on 20000401], DOI: 10.1016/S1388-2481(00)00011-4 * |
GOTZ M ET AL: "Binary and ternary anode catalyst formulations including the elements W, Sn and Mo for PEMFCs operated on methanol or reformate gas", ELECTROCHIMICA ACTA, ELSEVIER SCIENCE PUBLISHERS, BARKING, GB, vol. 43, no. 24, 21 August 1998 (1998-08-21), pages 3637 - 3644, XP004137719, ISSN: 0013-4686, DOI: 10.1016/S0013-4686(98)00121-2 * |
LIMA F H B ET AL: "Carbon-dispersed Pt-Rh nanoparticles for ethanol electro-oxidation. Effect of the crystallite size and of temperature", JOURNAL OF ELECTROANALYTICAL CHEMISTRY AND INTERFACIAL ELECTROCHEMISTRY, ELSEVIER, AMSTERDAM, NL, vol. 617, no. 2, 15 June 2008 (2008-06-15), pages 121 - 129, XP022674277, ISSN: 0022-0728, [retrieved on 20080208], DOI: 10.1016/J.JELECHEM.2008.01.024 * |
SANTIAGO E I ET AL: "CO tolerance on PtMo/C electrocatalysts prepared by the formic acid method", ELECTROCHIMICA ACTA, ELSEVIER SCIENCE PUBLISHERS, BARKING, GB, vol. 48, no. 23, 15 October 2003 (2003-10-15), pages 3527 - 3534, XP004453399, ISSN: 0013-4686, DOI: 10.1016/S0013-4686(03)00474-2 * |
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