WO2014131724A1 - Procede de synthese de particules de catalyseur bimetallique a base de platine et d'un autre metal et leur utilisation dans une méthode de production electrochimique d'hydrogene - Google Patents
Procede de synthese de particules de catalyseur bimetallique a base de platine et d'un autre metal et leur utilisation dans une méthode de production electrochimique d'hydrogene Download PDFInfo
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- WO2014131724A1 WO2014131724A1 PCT/EP2014/053535 EP2014053535W WO2014131724A1 WO 2014131724 A1 WO2014131724 A1 WO 2014131724A1 EP 2014053535 W EP2014053535 W EP 2014053535W WO 2014131724 A1 WO2014131724 A1 WO 2014131724A1
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- WO
- WIPO (PCT)
- Prior art keywords
- catalyst particles
- metal
- platinum
- bimetallic catalyst
- synthesizing
- Prior art date
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 239000002245 particle Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 29
- 239000002184 metal Substances 0.000 title claims abstract description 29
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 22
- 239000001257 hydrogen Substances 0.000 title claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 37
- 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 21
- 230000008014 freezing Effects 0.000 claims abstract description 7
- 238000007710 freezing Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 33
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 33
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 16
- 235000019253 formic acid Nutrition 0.000 claims description 11
- 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 10
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000002105 nanoparticle Substances 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 230000012010 growth Effects 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008246 gaseous mixture Substances 0.000 claims description 5
- 238000001833 catalytic reforming Methods 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 150000004767 nitrides Chemical class 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
- -1 compounds hydrocarbon Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 239000003738 black carbon Substances 0.000 claims 1
- 239000007789 gas Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000006056 electrooxidation reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 230000035784 germination Effects 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 230000009467 reduction Effects 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
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- 229910018941 Pt3Sn Inorganic materials 0.000 description 2
- 241000872198 Serjania polyphylla Species 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
- 230000000903 blocking effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane 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
- 230000001737 promoting effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 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
- 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
- 239000010405 anode material Substances 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 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
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000463 material Substances 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
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002923 metal particle Substances 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
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000011232 storage material Substances 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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- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Definitions
- the field of the invention is that of H 2 / O 2 fuel cells.
- pressurized hydrogen tanks gas storage
- metal hydrides storage in solid form
- 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.
- an electrochemical cell connected to a low-power power supply.
- 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 reaction of electro-oxidation of hydrogen (H 2 -> 2H + + 2e " ).
- Pt platinum
- Pt platinum
- This poisoning is done by adsorption of CO on the surface of the Pt irreversibly by blocking the available adsorption sites, thus preventing the adsorption of hydrogen, and its oxidation.
- Pt-Ru platinum-ruthenium
- Pt-Sn platinum-tin
- Pt-Mo platinum-molybdenum
- Pt-Co platinum-cobalt
- the present invention relates to 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 germination making it possible to increase the number of germs.
- 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 subject of the present invention is a process for synthesizing 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 at least one second salt or complex based on said second metal, said chemical reduction comprising the following steps:
- 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.
- the reducing agent is hydrazine, the temperature of said reduction being carried out at a temperature between 0 ° C. and 2 ° C.
- the reducing agent is formaldehyde, the temperature of said reduction being carried out at a temperature of between -19 ° C. and 0 ° C.
- 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.
- the amount of reducing agent is greater than or equal to the amount necessary to carry out the chemical reduction of all platinum salts and complexes and those of the second metal.
- the reaction is carried out in the presence of an additional source of energy to accelerate the chemical reduction operation without promoting the growth of nanoparticles.
- the additional energy source is a source of ultraviolet radiation.
- the source of ultraviolet radiation emits in a wavelength range of between about 200 nm and 300 nm.
- the second metal is tin, or ruthenium, or molybdenum, or cobalt.
- the bimetallic catalyst particles are based on platinum and tin and their size distribution has a median value of 4 nm with a low dispersion: the standard deviation is of the order of 1 , 1.
- the subject of the invention is also the use of the process for synthesizing bimetallic catalyst particles according to the invention, for a method of electrochemical hydrogen production comprising a catalytic reforming reaction in the presence of said catalyst particles and a mixture gas comprising hydrocarbon compounds.
- the metal particles obtained by the synthesis method of the invention appear in fact less sensitive to pollution by the hydrocarbon compounds present in the gas mixture than the particles obtained according to the methods described in the state of the art.
- the gaseous mixture comprises carbon monoxide, carbon dioxide and methane.
- FIG. 1 illustrates the UV absorption spectra of the PtCl 6 2 - ions
- FIG. 2 illustrates the particle size distribution of the Pt 3 Sn / C catalysts synthesized at room temperature and at 4 ° C., according to the process of the invention
- FIG. 3 illustrates the cyclic voltammogram obtained on Pt 3 Sn / C synthesized at room temperature in an aqueous solution of H 2 SO 4 at a concentration of 0.5 M at 25 ° C .;
- FIG. 4 illustrates the cyclic voltammogram obtained on Pt 3 Sn / C synthesized at 4 ° C. in an aqueous solution of H 2 SO 4 at a concentration of 0.5 M at 25 ° C .;
- FIG. 5 illustrates the evolution of the electro-oxidation current of H 2 on Pt 3 Sn / C synthesized at ambient temperature and at 4 ° C. in an aqueous solution of H 2 SO 4 of concentration 0.5 M after having subjected the catalyst to a mixture of compound gas 50 ppm CO in H 2 and 0.24 V vs. ERH and reaches a quasi stationary state of evolution of the oxidation current of hydrogen over time.
- Pt-M platinum-metal alloy
- Applicant uses the method FAM (Formic Acid Method) as described in the article E.l. Santiago et al. "CO tolerance on PtMo / C electrocatalysts prepared by the formic acid method" Electrochimica Acta 48 (2003) 3527-3534.
- solutions of salts or complexes of Pt and a metal alloy as precursors of Pt-M catalysts supported or not on carbon black with a high specific surface area, a metal oxide (TiO 2 2 , ZrO 2 , Al 2 O 3 , ...) or metal nitrides (TiN, TaN, BN), metal carbides (TiC, WC, W 2 C, Mo 2 C, etc.).
- the solutions of salts or complexes of Pt and the alloy metal element M are mixed with the carbon support and the whole is shaken vigorously with ultrasound for at least half an hour , time necessary 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 salts or metal 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 lengthens the duration of chemical reduction of the metal salts. To overcome this lengthening of duration, it is appropriate to accelerate the chemical reduction reaction without increasing the rate of growth.
- the vial containing the mixture may advantageously be exposed to a source of energy, for example ultraviolet (UV) rays which make it possible, thanks to this energy supply, to accelerate the reaction (the germination of the particles), thus favoring the multiplicity of seeds. in the nanoparticular state without promoting their growth.
- a source of energy for example ultraviolet (UV) rays which make it possible, thanks to this energy supply, to accelerate the reaction (the germination of the particles), thus favoring the multiplicity of seeds. in the nanoparticular state without promoting their growth.
- UV rays which make it possible, thanks to this energy supply, to accelerate the reaction (the germination of the particles), thus favoring the multiplicity of seeds. 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.
- Embodiment Pt-Sn / C catalysts of 3: 1 molar composition were synthesized by chemical reduction with formic acid.
- Aqueous solutions of platinum and tin salts of 0.01 M concentration were mixed in the presence of carbon black and vigorously shaken with ultrasound for a period of about one hour.
- the volumes of K 2 PtCl 6 , 6H 2 0 and SnCl 2 , 2H 2 0 solutions mixed are respectively 15 ml and 5 ml so as to obtain an atomic ratio of 3: 1.
- 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.
- 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 electro-active surface corresponds more precisely to the electro-chemically active surface for the reactions considered, which one seeks to increase.
- Figure 2 illustrates particle size distributions of Pt 3 Sn / C catalysts synthesized at room temperature (25 ° C) and at 4 ° C and demonstrates the high percentage of small particles, typically 3 to 4 nm. with the synthesis method of the invention.
- EDS Energy Dispersive X-ray Spectrometry
- the electroactive surface of the catalyst prepared at 4 ° C. is thus much larger than that of the same catalyst synthesized at 25 ° C.
- the Applicant has carried out the cyclic voltammograms in an electrochemical half-cell at 25 ° C. with a scanning speed of 10 mV / s, relative to the various catalysts prepared.
- cyclic voltammetry is a method of electrochemical analysis 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 helps identify and measure quantitatively a large number of compounds and also to study the chemical reactions including these compounds.
- the high absorption power can be characterized by the absence of oxidation peaks (positive current) on the voltammogram having the measured current density as a function of the applied potential E to the working electrode.
- the absence of these peaks on the voltammogram reflects the blocking of adsorption sites of the catalyst by another species.
- Figure 3 relates to the results obtained with Pt 3 Sn / C particles prepared at 25 ° C.
- Curve 3a is relative to the voltammetric curve (under N 2 , in 0.5 MH 2 SO 4 at 25 ° C. and 10 mV.s.sup.- 1 ) carried out after pollution of the catalyst by adsorption of CO.
- Figure 4 relates to the results obtained with Pt 3 Sn / C particles prepared at 4 ° C.
- curve 4a the same cyclic voltammetric curve after pollution of the catalyst by CO adsorption shows that the pollution of the catalyst is not complete: the hydrogen desorption peaks are still observed.
- curve 4a between 0.1 and 0.4 V vs. ERH and oxidation of CO starts at an electrode potential of 0.3 V vs. ERH.
- the gain, in terms of energy, for the oxidation of hydrogen in the presence of traces of polluting gases is nearly 30% (0.72 kWh / Nm 3 H 2 with the catalyst synthesized at 4 ° C, against 0, 96 kWi // Nm 3 H 2 with the catalyst synthesized at 25 ° C).
- the Applicant has also followed the evolution of the electro-oxidation current of H 2 on Pt 3 Sn / C synthesized at room temperature and at 4 ° C. in an electrochemical half-cell device, when the electrode is fed with a mixture gas composed of 50 ppm CO in H 2 and subjected to a potential of 0.24 V vs. ERH.
- FIG. 5 shows via the curves 5a and 5b the difference in behavior with a catalyst produced according to the present invention at a temperature of 4 ° C., compared to a catalyst produced at ambient temperature.
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Abstract
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Priority Applications (3)
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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 |
EP14706561.9A EP2961527A1 (fr) | 2013-02-26 | 2014-02-24 | Procede de synthese de particules de catalyseur bimetallique a base de platine et d'un autre metal et leur utilisation dans une méthode de production electrochimique d'hydrogene |
JP2015558484A JP2016513013A (ja) | 2013-02-26 | 2014-02-24 | 白金と別の金属とでできたバイメタル触媒粒子の合成方法、および電気化学的水素製造方法におけるその使用 |
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FR1351679 | 2013-02-26 | ||
FR1351679A FR3002464A1 (fr) | 2013-02-26 | 2013-02-26 | Procede de synthese de particules de catalyseur bimetallique a base de platine et d'un autre metal et methode de production electrochimique d'hydrogene utilisant ledit procede de synthese |
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EP (1) | EP2961527A1 (fr) |
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CN109014238A (zh) * | 2018-05-24 | 2018-12-18 | 清华大学 | 一种低温液相合成高性能金属材料的方法 |
Citations (2)
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EP0091165A1 (fr) * | 1982-04-01 | 1983-10-12 | Nederlandse Organisatie Voor Zuiver-Wetenschappelijk Onderzoek (ZWO) | Catalyseur à base d'argent et procédé pour la préparation de celui-ci |
WO2005063390A1 (fr) * | 2003-12-25 | 2005-07-14 | Nissan Motor Co., Ltd. | Catalyseur en poudre, catalyseur de purification des gaz d'echappement, et procede permettant la production d'un catalyseur en poudre |
-
2013
- 2013-02-26 FR FR1351679A patent/FR3002464A1/fr active Pending
-
2014
- 2014-02-24 US US14/767,267 patent/US20160010229A1/en not_active Abandoned
- 2014-02-24 EP EP14706561.9A patent/EP2961527A1/fr not_active Withdrawn
- 2014-02-24 WO PCT/EP2014/053535 patent/WO2014131724A1/fr active Application Filing
- 2014-02-24 JP JP2015558484A patent/JP2016513013A/ja active Pending
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EP0091165A1 (fr) * | 1982-04-01 | 1983-10-12 | Nederlandse Organisatie Voor Zuiver-Wetenschappelijk Onderzoek (ZWO) | Catalyseur à base d'argent et procédé pour la préparation de celui-ci |
WO2005063390A1 (fr) * | 2003-12-25 | 2005-07-14 | Nissan Motor Co., Ltd. | Catalyseur en poudre, catalyseur de purification des gaz d'echappement, et procede permettant la production d'un catalyseur en poudre |
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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 * |
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FR3002464A1 (fr) | 2014-08-29 |
EP2961527A1 (fr) | 2016-01-06 |
US20160010229A1 (en) | 2016-01-14 |
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