TWI508774B - Production method for gold-supported carbon catalyst - Google Patents
Production method for gold-supported carbon catalyst Download PDFInfo
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- TWI508774B TWI508774B TW102120076A TW102120076A TWI508774B TW I508774 B TWI508774 B TW I508774B TW 102120076 A TW102120076 A TW 102120076A TW 102120076 A TW102120076 A TW 102120076A TW I508774 B TWI508774 B TW I508774B
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- gold
- liquid
- catalyst
- carbon catalyst
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- 239000003054 catalyst Substances 0.000 title claims description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 46
- 229910052799 carbon Inorganic materials 0.000 title claims description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 123
- 239000010931 gold Substances 0.000 claims description 122
- 229910052737 gold Inorganic materials 0.000 claims description 122
- 239000002245 particle Substances 0.000 claims description 107
- 239000007788 liquid Substances 0.000 claims description 79
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 230000003068 static effect Effects 0.000 claims description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 239000003146 anticoagulant agent Substances 0.000 claims description 3
- 229940127219 anticoagulant drug Drugs 0.000 claims description 3
- 229940072107 ascorbate Drugs 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 2
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 claims 4
- 239000008187 granular material Substances 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 68
- 229910052697 platinum Inorganic materials 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 15
- 239000000446 fuel Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 239000012279 sodium borohydride Substances 0.000 description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000011162 core material Substances 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000001509 sodium citrate Substances 0.000 description 4
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 4
- 229940038773 trisodium citrate Drugs 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- LUVOJBWJNHWVNG-UHFFFAOYSA-N [Na].[Na].[Na].OC(=O)CC(O)(C(O)=O)CC(O)=O Chemical compound [Na].[Na].[Na].OC(=O)CC(O)(C(O)=O)CC(O)=O LUVOJBWJNHWVNG-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003006 anti-agglomeration agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical class Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- ZWZLRIBPAZENFK-UHFFFAOYSA-J sodium;gold(3+);disulfite Chemical compound [Na+].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O ZWZLRIBPAZENFK-UHFFFAOYSA-J 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000019263 trisodium citrate Nutrition 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
- B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
-
- 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
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- B01J35/23—
-
- B01J35/393—
-
- B01J35/40—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8842—Coating using a catalyst salt precursor in solution followed by evaporation and reduction of the precursor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9058—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of noble metals or noble-metal based alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Description
本發明係有關於一種擔持金之碳觸媒及其製造方法。特別是提供一種適合於固體高分子型的燃料電池用途且有助於減低鉑使用量之擔持金之碳觸媒。The present invention relates to a carbon catalyst for supporting gold and a method for producing the same. In particular, it is possible to provide a carbon catalyst suitable for use in a solid polymer type fuel cell and which contributes to reducing the amount of platinum used.
燃料電池係高度期待作為下世代的發電系統，特別是一種將固體高分子使用作為電解質之固體高分子型的燃料電池，因為相較於磷酸型燃料電池等之動作溫度較低且小型化，而被期望利用作為電動汽車用的電源。The fuel cell system is highly expected as a power generation system for the next generation, and in particular, a solid polymer fuel cell using a solid polymer as an electrolyte, because the operating temperature is lower and smaller than that of a phosphoric acid fuel cell. It is expected to be utilized as a power source for electric vehicles.
為了促進電化學反應，該等固體高分子型燃料電池係使用觸媒與固體高分子的混合體作為電極。而且，通常已知之作為電極所使用的觸媒，係使碳粉末等的導電性物質擔持鉑而成者作為觸媒成分。因為使用鉑之觸媒係觸媒能力高且在寬闊的電位範圍中穩定地起作用。In order to promote an electrochemical reaction, these solid polymer fuel cells use a mixture of a catalyst and a solid polymer as an electrode. In addition, a catalyst used as an electrode is generally known as a catalyst component in which a conductive material such as carbon powder is supported by platinum. Because of the high catalytic capacity of the catalyst using platinum, it acts stably in a wide potential range.
但是，因為貴金屬之中鉑係特別昂貴，而成為燃料電池成本高的主要原因，而被要求開發經減低鉑的使用量之觸媒。專利文獻1係記載藉由使用價廉的金屬氧化物等而使鉑的使用量減低之觸媒，專利文獻2係記載 藉由使鉑粒子的平均粒徑為比碳粉末的微細孔徑更大而防止鉑粒子進入微細結構內，來提升鉑的利用效率之技術。However, since platinum is particularly expensive among precious metals, it is a major cause of high cost of fuel cells, and it is required to develop a catalyst that reduces the amount of platinum used. Patent Document 1 describes a catalyst for reducing the amount of platinum used by using an inexpensive metal oxide or the like, and Patent Document 2 describes A technique for improving the utilization efficiency of platinum by making the average particle diameter of the platinum particles larger than the fine pore diameter of the carbon powder to prevent the platinum particles from entering the fine structure.
專利文獻Patent literature
[專利文獻1] 日本特開2010-92725號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-92725
[專利文獻2] 日本特開2007-250274號公報[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-250274
[非專利文獻][Non-patent literature]
[非專利文獻3] I.Park,K.Lee,D.Jung,H.Park,Y.Sung,Electrochem.Acta,50(2007),5599[Non-Patent Document 3] I. Park, K. Lee, D. Jung, H. Park, Y. Sung, Electrochem. Acta, 50 (2007), 5599
依照上述先前技術記載的觸媒雖然能夠減低鉑的使用量，但是相較於只有使用鉑之觸媒，實際上使用作為燃料電池的電極時有觸媒能力低且耐久性差之情形。因此，本發明的目的係提供一種觸媒，其係適合於固體高分子型燃料電池之觸媒，能夠減低鉑的使用量，同時能夠實現與只使用鉑時相同的觸媒能力和耐久性。Although the catalyst described in the above prior art can reduce the amount of platinum used, compared with a catalyst using only platinum, the use of an electrode as a fuel cell actually has a low catalyst capacity and poor durability. Accordingly, it is an object of the present invention to provide a catalyst which is suitable for a catalyst for a polymer electrolyte fuel cell, which can reduce the amount of platinum used and at the same time achieve the same catalytic ability and durability as when only platinum is used.
作為解決上述課題之觸媒，本發明者等係著眼於使碳擔體擔持金粒子而成之擔持金之碳觸媒作為鉑觸媒的前驅材料，並藉由在該金粒子上積層鉑粒子而成之二層構造，而能夠減低鉑的使用量。而且，為了實現與只 擔持鉑粒子之觸媒相同的觸媒能力，針對此種擔持金之觸媒的物性進行專心研討，發現最適合的金粒子之形態並從而想出本發明。As a catalyst for solving the above problems, the inventors of the present invention focused on a gold-based carbon catalyst in which a gold carrier is supported by gold as a precursor of a platinum catalyst, and laminated on the gold particles. The platinum layer is a two-layer structure that reduces the amount of platinum used. And, in order to achieve By carrying out the same catalytic ability as the catalyst of the platinum particles, the physical properties of the gold-bearing catalyst were intensively studied, and the most suitable form of the gold particles was found, and the present invention was conceived.
亦即，本發明係有關於一種擔持金之碳觸 媒，其係在作為擔體之碳上擔持金粒子而成之觸媒，其中，金粒子係平均粒徑2.0nm至6.0nm且粒徑的標準偏差為30%以內。使用擔持有如此微細且粒徑分布集中且偏差少的金粒子之觸媒時，與只有擔持鉑粒子之觸媒相同的觸媒能力之同時，能夠減低鉑的使用量。That is, the present invention relates to a carbon touch that carries gold The medium is a catalyst in which gold particles are supported on carbon as a support, wherein the gold particles have an average particle diameter of 2.0 nm to 6.0 nm and a standard deviation of particle diameters of 30% or less. When a catalyst having such a fine particle particle size distribution and small variation of gold particles is used, the same catalyst capacity as that of the catalyst supporting the platinum particles can be used, and the amount of platinum used can be reduced.
本發明的觸媒，較佳是被擔體擔持的金粒 子之平均粒徑為2.0nm至6.0nm的範圍內，且作為核殼觸媒的核材之平均粒徑為3.0nm至5.0nm。小於2.0nm時，在金粒子上積層鉑時，鉑在酸性環境下有溶出的可能性。超過6.0nm時，無法得到作為反應場(reaction field)之表面積，致使觸媒能力容易降低。又，金粒子粒徑之標準偏差為30%以內。標準偏差超過30%時，因為粒徑係成為偏頗的狀態，之後使鉑粒子在金粒子上析出時有無法得到穩定性能之可能性。又，作為平均粒徑的算出方法，藉由X射線繞射係簡便的。又，作為粒徑標準偏差之算出方法，可從使用透射型電子顯微鏡(TEM)之照片(較佳是使用複數張之3至5張)選出任意個數(較佳為200至300個)的粒子並測定粒徑而求取。The catalyst of the present invention is preferably a gold particle supported by a carrier. The average particle diameter of the sub-particles is in the range of 2.0 nm to 6.0 nm, and the average particle diameter of the core material as the core-shell catalyst is 3.0 nm to 5.0 nm. When it is less than 2.0 nm, when platinum is laminated on gold particles, platinum may be eluted in an acidic environment. When it exceeds 6.0 nm, the surface area as a reaction field cannot be obtained, and the catalyst ability is easily lowered. Further, the standard deviation of the particle diameter of the gold particles is within 30%. When the standard deviation exceeds 30%, the particle size is in a biased state, and there is a possibility that the platinum particles are not precipitated when they are precipitated on the gold particles. Further, as a method of calculating the average particle diameter, the X-ray diffraction system is simple. Further, as a method of calculating the standard deviation of the particle diameter, any number (preferably 200 to 300) can be selected from a photograph using a transmission electron microscope (TEM) (preferably, using 3 to 5 sheets of plural sheets). The particles were determined by measuring the particle size.
本發明之擔持金之觸媒係鉑粒子在金粒子 上析出之觸媒，藉此亦能夠利用作為固體高分子型的燃料 電池用核殼觸媒。該擔持金之觸媒之金的擔持率較佳係10至70%，更佳是20至60%。金的擔持率為10%以下時鉑析出之反應場會消失，而70%以上時金粒子彼此凝聚故使作為核材的功能消失。若在上述範圍內，則可為在減低鉑使用量下觸媒能力及耐久性為與只擔持鉑時相同程度之觸媒。又，本發明之擔體上的金粒子，係使平均粒徑、粒徑分布適當化且設為上述的擔持率，藉此使其本身亦具有觸媒活性。The gold-bearing catalyst of the present invention is a platinum particle in a gold particle The catalyst that is deposited on it can also be used as a solid polymer fuel. Core shell catalyst for batteries. The holding ratio of the gold-bearing catalyst is preferably 10 to 70%, more preferably 20 to 60%. When the gold holding ratio is 10% or less, the reaction field in which platinum is precipitated disappears, and when 70% or more, the gold particles are agglomerated, so that the function as a core material disappears. If it is in the above range, the catalyst ability and durability at the time of reducing the amount of platinum used may be the same as that of the case where only platinum is supported. Moreover, the gold particles on the support of the present invention have an average particle diameter and a particle size distribution, and have the above-described support ratio, thereby providing catalyst activity as well.
其次針對本發明之擔持金之碳觸媒的製造 方法進行說明。本發明之擔持金之觸媒較佳為將金鹽的水溶液還原處理而析出金粒子並使擔體接觸該反應液而擔持金粒子之方法。本發明之擔持金之觸媒，係在碳擔體表面均勻地分散擔持微細的金粒子者，且較佳為擔持至擔體的細孔內部。就此點而言，作為金粒子的擔持形態，雖然亦可考慮在擔體吸附擔持另外製造之粒子狀態的金之方法，但是此種另外製造的金粒子係需要用以確保金粒子的安定性之保護劑，含有此種保護劑的金粒子係難以侵入擔體的細孔。在本發明中，係將使金鹽溶液與還原劑混合而還原金之反應液緊接著與擔體接觸，藉此使只由金所構成的微細粒子侵入至細孔，而能夠製成均勻地擔持金粒子之擔持金之碳觸媒。Secondly, the manufacture of the carbon catalyst supporting the gold of the present invention The method is explained. The gold-carrying catalyst of the present invention is preferably a method in which an aqueous solution of a gold salt is subjected to a reduction treatment to precipitate gold particles, and the carrier is brought into contact with the reaction liquid to carry the gold particles. The gold-carrying catalyst of the present invention is obtained by uniformly dispersing and holding fine gold particles on the surface of the carbon support, and is preferably carried inside the pores of the support. In this regard, as the supporting form of the gold particles, it is also conceivable to adsorb the gold in the state of the particles to be separately produced in the support, but the gold particles to be separately produced are required to secure the stability of the gold particles. The protective agent of the nature, the gold particles containing such a protective agent are difficult to intrude into the pores of the support. In the present invention, the reaction solution in which the gold salt solution and the reducing agent are mixed to reduce the gold is brought into contact with the carrier, whereby fine particles composed of only gold are intruded into the pores, and uniformity can be obtained. The carbon catalyst that is responsible for the gold particles.
而且，使用還原析出法來製造本發明之擔 持金之觸媒時，使金的還原以均勻且適當的反應速度進行係重要的。係因為了製成如本發明之平均粒徑為2.0nm至 6.0nm之微細的金粒子，在其製造步驟中必須設為金粒子特別容易進行凝聚和沈澱之條件，特別是在還原步驟中必須設為容易形成微粒且偏差少的金粒子之條件。作為此種還原步驟可考慮例如邊以高速攪拌反應溶液邊使其反應之方法等，但是此種實驗室的方法可以說不適合於工業規模生產。Moreover, the reduction precipitation method is used to manufacture the burden of the present invention. In the case of a gold-bearing catalyst, it is important to carry out the reduction of gold at a uniform and appropriate reaction rate. Because the average particle diameter as in the present invention is 2.0 nm to The fine gold particles of 6.0 nm are required to be a condition in which the gold particles are particularly likely to be aggregated and precipitated in the production step, and in particular, it is necessary to set the conditions of the gold particles which are easy to form fine particles and have little variation in the reduction step. As such a reduction step, for example, a method in which a reaction solution is stirred while stirring at a high speed or the like can be considered, but such a laboratory method can be said to be unsuitable for industrial scale production.
本發明者等針對能夠確實且有效率地製造 微細且粒徑趨於一致的金粒子之方法而進行專心研討。結果想到包含以下步驟之製造方法：調製含有金鹽與抗凝聚劑之A液及含有還原劑與抗凝聚劑之B液之步驟；使所調製的A液及B液在靜力混合器中進行反應而使金還原之步驟；以及使金還原後使作為擔體之碳接觸A液與B液的混合液，而使其擔持金之步驟。以下，針對上述製造方法而詳細地說明。The inventors of the present invention are directed to being able to manufacture reliably and efficiently Concentrate on the method of fine and uniform gold particles. As a result, a manufacturing method including the following steps is prepared: a step of preparing a liquid A containing a gold salt and an anti-agglomerating agent, and a liquid B containing a reducing agent and an anti-agglomerating agent; and the prepared liquid A and liquid B are carried out in a static mixer. a step of reducing the gold by the reaction; and a step of bringing the carbon as the support into contact with the mixture of the liquid A and the liquid B to carry the gold. Hereinafter, the above production method will be described in detail.
首先，針對A液進行說明。作為金鹽的種 類，係能夠應用氯化金、氯金酸、亞硫酸金鈉等。該等金鹽的含量，係在A液中以設為0.10至0.80mM的範圍內為佳。因在該範圍內時容易形成平均粒徑2.0至6.0nm且均勻的金粒子。小於0.10mM時，不容易形成均勻的金粒子，超過0.80mM時，有難以製成平均粒徑6nm以下的金粒子之傾向。又，A液係能夠使用酸性溶液、鹼性溶液、或純水作為溶劑。First, the liquid A will be described. As a species of gold salt For the class, it is possible to apply gold chloride, chloroauric acid, gold sodium sulfite, and the like. The content of these gold salts is preferably in the range of 0.10 to 0.80 mM in the liquid A. When it is within this range, gold particles having an average particle diameter of 2.0 to 6.0 nm and uniform are easily formed. When it is less than 0.10 mM, it is difficult to form uniform gold particles, and when it exceeds 0.80 mM, it is difficult to form gold particles having an average particle diameter of 6 nm or less. Further, the A liquid system can use an acidic solution, an alkaline solution, or pure water as a solvent.
為了防止金的凝聚而使其形成微細的金粒 子，A液係含有抗凝聚劑。作為抗凝聚劑，係能夠應用檸 檬酸、檸檬酸三鈉等的檸檬酸鹽、以及抗壞血酸鹽、聚乙烯基吡咯啶酮(polyvinyl pyrrolidone)、聚乙烯亞胺、聚丙烯酸、四甲銨。較佳是檸檬酸、檸檬酸鹽。抗凝聚劑濃度係相對於金鹽濃度，能夠以莫耳比計為2至15倍為止對應，較佳是6至12倍。小於2倍時，金粒子係難以吸附在碳上，超過15倍時，金粒子有粗大化之傾向。In order to prevent the aggregation of gold, it forms fine gold particles. The A liquid system contains an anti-agglomerating agent. As an anti-agglomerating agent, it is capable of applying lemon Citrate such as citric acid or trisodium citrate, as well as ascorbate, polyvinyl pyrrolidone, polyethyleneimine, polyacrylic acid, and tetramethylammonium. Preferred are citric acid and citrate. The concentration of the anti-agglomeration agent can be 2 to 15 times in terms of the molar ratio with respect to the concentration of the gold salt, and is preferably 6 to 12 times. When it is less than 2 times, it is difficult for gold particles to adsorb on carbon, and when it exceeds 15 times, gold particles tend to coarsen.
其次，針對B液進行說明。作為在B液所 含的還原劑，係能夠應用氫化硼鈉(SBH)、肼、甲酸鈉、醇等，但以SBH為佳。上述還原劑的含量係在B液中設為0.1至5.0mM。小於0.1mM時，不容易形成均勻的金粒子，超過5.0mM時，金粒子之間容易產生凝聚。較佳條件為0.3至3.0mM的範圍內。又，B液係能夠使用鹼溶液或純水作為溶劑。Next, the liquid B will be described. As in B liquid The reducing agent to be contained may be sodium borohydride (SBH), hydrazine, sodium formate, alcohol or the like, but SBH is preferred. The content of the above reducing agent is set to 0.1 to 5.0 mM in the liquid B. When it is less than 0.1 mM, uniform gold particles are not easily formed, and when it exceeds 5.0 mM, aggregation of gold particles is likely to occur. Preferred conditions are in the range of 0.3 to 3.0 mM. Further, the B liquid system can use an alkali solution or pure water as a solvent.
在本發明之擔持金之觸媒的製造方法，不 僅是上述的A液，在B液亦必須含有抗凝聚劑。藉由使B液亦含有抗凝聚劑，金的還原係均勻且以適當的反應速度進行。作為抗凝聚劑，係與A液相同地，除了能夠使用檸檬酸、檸檬酸三鈉等的檸檬酸鹽以外，可使用抗壞血酸鹽、聚乙烯基吡咯啶酮、聚乙烯亞胺、聚丙烯酸、四甲銨等。 較佳為檸檬酸、檸檬酸鹽。抗凝聚劑的莫耳濃度係相對於還原劑的莫耳濃度，以莫耳比計在0.2至1.5倍的範圍內為佳。小於0.2倍時金不會還原且從擔體脫落掉，超過1.5倍時粒子產生粗大化。In the method for manufacturing a catalyst for supporting gold according to the present invention, It is only the above liquid A, and the liquid B must also contain an anti-agglomerating agent. By also including the anti-coagulant in the liquid B, the reduction of gold is uniform and proceeds at an appropriate reaction rate. As the anti-agglomerating agent, in the same manner as the liquid A, in addition to citrate such as citric acid or trisodium citrate, ascorbate, polyvinylpyrrolidone, polyethyleneimine, polyacrylic acid, or the like can be used. Methylammonium and the like. Preferred are citric acid and citrate. The molar concentration of the anti-agglomerating agent is preferably in the range of 0.2 to 1.5 times the molar ratio with respect to the molar concentration of the reducing agent. When the amount is less than 0.2 times, the gold is not reduced and falls off from the support, and when it exceeds 1.5 times, the particles are coarsened.
其次，針對將以上說明的A液及B液混合 而使金還原之步驟進行說明。金的還原步驟中，混合A液與B液使用靜力混合器。根據靜力混合器而可以短時間穩定且高均勻度地將A液與B液混合，故可每次少量迅速地使金的還原反應均勻地進行。作為靜力混合器，在內部所導入的靜力混合器係以使用6葉片(element)以上且30葉片以下者為佳。小於上述葉片數時，有A液與B液的混合不充分且粒徑的偏差變大之傾向。又，超過上述葉片數時，有裝置大型化之可能性。更佳為10葉片以上且25葉片以下。Secondly, for mixing the liquid A and liquid B described above The steps of gold reduction are explained. In the gold reduction step, a static mixer is used to mix the A liquid and the B liquid. According to the static mixer, the liquid A and the liquid B can be mixed stably for a short period of time and high uniformity, so that the reduction reaction of gold can be performed uniformly in a small amount at a time. As the static mixer, the static mixer introduced inside is preferably six or more elements and 30 or less blades. When the number of the blades is less than the number of the above-mentioned blades, the mixing of the A liquid and the B liquid is insufficient, and the variation in the particle diameter tends to be large. Moreover, when the number of the above-mentioned blades is exceeded, there is a possibility that the device is enlarged. More preferably, it is 10 or more blades and 25 or less blades.
在以上之金的還原步驟，以使A液與B液 (A液：B液)以1：1至1：5的流量比例混合為佳。該範圍內時，能夠以適當的反應速度使金進行還原。A液的送液量太多時，有難以製成平均粒徑6.0nm以下的金粒子之傾向，B液的送液量太多時，有難以使還原反應均勻地進行之傾向。更佳為1：2至1：3。In the above gold reduction step, so that liquid A and liquid B (A liquid: liquid B) is preferably mixed at a flow ratio of 1:1 to 1:5. Within this range, gold can be reduced at an appropriate reaction rate. When the liquid supply amount of the liquid A is too large, it is difficult to form gold particles having an average particle diameter of 6.0 nm or less. When the liquid supply amount of the liquid B is too large, it is difficult to uniformly carry out the reduction reaction. More preferably 1:2 to 1:3.
在本發明的製造方法中，在將A液與B液 混合而使金進行還原之溶液，隨後使擔體之碳接觸該溶液而使其擔持金。如此，藉由先還原金後使擔體擔持金，而能夠將粒徑均勻的金粒子固定在擔體上。又，混合液與碳的接觸，較佳是將碳分散液投入至混合液而使混合液含浸碳。In the manufacturing method of the present invention, the liquid A and the liquid B are The solution in which the gold is reduced is mixed, and then the carbon of the support is brought into contact with the solution to support the gold. In this manner, the gold particles having a uniform particle diameter can be fixed to the support by first reducing the gold and then supporting the gold. Further, in the contact of the mixed solution with carbon, it is preferred to introduce the carbon dispersion into the mixed solution to impregnate the mixed solution with carbon.
依照本發明，藉由擔持微細且偏差少的金粒子而成之擔持金之碳觸媒，能夠提供一種在減低鉑的使 用量之同時，能夠實現與只使用鉑時相同的觸媒能力和耐久性之燃料電池用觸媒。According to the present invention, it is possible to provide a reduction in platinum by supporting a gold-based carbon catalyst which is made of fine and less variable gold particles. At the same time as the amount of use, it is possible to realize a catalyst for a fuel cell which has the same catalytic ability and durability as when only platinum is used.
擔持有本發明之金粒子之觸媒，係能夠藉由擔持鉑而作為燃料電池用觸媒。此時，藉由在氯鉑酸等的鉑鹽溶液浸漬本發明之觸媒，而使鉑粒子在金粒子上析出，能夠利用作為固體高分子型的燃料電池用觸媒。The catalyst for holding the gold particles of the present invention can be used as a catalyst for a fuel cell by supporting platinum. In this case, by impregnating the catalyst of the present invention with a platinum salt solution such as chloroplatinic acid, the platinum particles are precipitated on the gold particles, and a catalyst for a fuel cell as a solid polymer type can be used.
第1圖係實施例1所合成的金奈米粒子之電子顯微鏡影像。Fig. 1 is an electron microscope image of the gold nanoparticles synthesized in Example 1.
第2圖係實施例1所合成的金奈米粒子之粒徑分布的測定結果。Fig. 2 is a measurement result of the particle size distribution of the gold nanoparticles synthesized in Example 1.
第3圖係實施例1、比較例1之擔持金之觸媒所製成的電極之氫氧化活性的測定結果。Fig. 3 is a graph showing the measurement results of the hydrogenation activity of the electrode prepared by the catalyst for carrying gold in Example 1 and Comparative Example 1.
以下說明本發明之最佳實施形態。Preferred embodiments of the present invention are described below.
[第一實施形態]：在此，變更有無使用靜力混合器、作為擔體之碳的添加順序，而製造擔持金之觸媒，且測定所得到的觸媒之金粒子粒徑等。[First Embodiment] Here, the presence or absence of the use of a static mixer and the addition of carbon as a support is performed, and a catalyst for supporting gold is produced, and the particle size of the gold particles of the obtained catalyst is measured.
實施例1Example 1
(各混合液的調製)(modulation of each mixture)
一邊使用化學混合機攪拌5L純水一邊添加0.61g之金含量48%的氯金酸、2.5g之純度99%的二水合檸檬酸三鈉，調製含有0.29mM的氯化金鹽、1.70mM(0.05wt%)的檸檬酸 三鈉之A液。同樣地，一邊攪拌15L純水一邊添加0.51g之純度92%的氫化硼鈉(SBH)、2.5g之純度99%的二水合檸檬酸三鈉，調製含有0.83mM的SBH、0.57mM(0.02wt%)的檸檬酸三鈉之B液。While stirring 5 L of pure water using a chemical mixer, 0.61 g of chloroauric acid having a gold content of 48% and 2.5 g of trisodium citrate dihydrate having a purity of 99% were added to prepare a gold chloride salt containing 0.29 mM and 1.70 mM ( 0.05 wt%) of citric acid Trisodium A solution. Similarly, 0.51 g of sodium borohydride (SBH) having a purity of 92% and 2.5 g of trisodium citrate dihydrate having a purity of 99% were added while stirring 15 L of pure water to prepare SBH containing 0.83 mM, 0.57 mM (0.02 wt.). %) Trisodium citrate solution B.
(金粒子液的合成及在碳之擔持)(Synthesis of gold particle liquid and its support in carbon)
將所調製的A液及B液，以A液500mL/min、B液1000mL/min的流量之方式(A液：B液=1：2)，使用長度13.5cm(葉片數：20個)的靜力混合器進行混合而使金還原。混合液係使用20L的琺瑯製槽收容，且槽內的溶液係使用攪拌機(攪拌速度200rpm)進行攪拌。又，反應溫度係設為25℃。在混合後的溶液，添加0.43g碳擔體(科琴碳黑(KETJEN BLACK)EC比表面積800m2 /g)而使其反應約3小時，使碳擔體上擔持金粒子。隨後，進行抽吸過濾且使用純水容器(vessel)進行洗淨3次之後，在60℃的大氣壓乾燥機使其乾燥一個白天而得到擔持金之碳觸媒。The prepared liquid A and liquid B were used in a flow rate of 500 mL/min of liquid A and 1000 mL/min of liquid B (liquid A: liquid B: 1:2), and the length was 13.5 cm (number of blades: 20). The static mixer is mixed to restore the gold. The mixed liquid was stored in a 20 L crucible tank, and the solution in the tank was stirred using a stirrer (stirring speed: 200 rpm). Further, the reaction temperature was set to 25 °C. To the mixed solution, 0.43 g of a carbon support (KETJEN BLACK EC specific surface area: 800 m 2 /g) was added and reacted for about 3 hours to carry gold particles on the carbon support. Subsequently, suction filtration was carried out and washed with a pure water vessel for 3 times, and then dried at 60 ° C in an atmospheric pressure dryer for one day to obtain a gold-bearing carbon catalyst.
比較例1Comparative example 1
除了將A液與B液不使用利用靜力混合器之反應系統，而使用化學混合機(攪拌速度800rpm)進行混合以外，使用與實施例1相同的製造方法製造觸媒。A catalyst was produced using the same production method as in Example 1 except that the liquid A and the liquid B were mixed without using a reaction system using a static mixer, and the mixture was mixed using a chemical mixer (stirring speed: 800 rpm).
比較例2Comparative example 2
除了將A液與B液，不使用利用靜力混合器之反應系統，而使用化學混合機(攪拌速度300rpm)進行混合以外，使用與實施例1相同的製造方法製造觸媒。The catalyst was produced in the same manner as in Example 1 except that the liquid A and the liquid B were mixed without using a reaction system using a static mixer and a chemical mixer (stirring speed: 300 rpm).
比較例3Comparative example 3
在金還原前添加碳粉末。除了預先在收容A液與B液的混合液之容器部分中，添加使用膠體研磨機(colloid mill)而為高分散之碳液，之後再於靜力混合器混合A液及B液以外，使用與實施例1相同的製造方法製造觸媒。Add carbon powder before gold reduction. In addition, in the container portion in which the mixed solution of the liquid A and the liquid B is contained, a colloid mill is used to add a highly dispersed carbon liquid, and then the mixture is mixed with the liquid A and the liquid B in a static mixer. The catalyst was produced in the same manner as in Example 1.
針對在以上的實施例及比較例所得的觸媒，進行粉末X射線繞射測定，且從波峰的繞射角及其半值寬度藉由雪萊公式(Scherrer’s formula)算出平均粒徑。又，進行TEM觀察(加速電壓200KeV、倍率20萬倍)，且從所拍攝的5張照片選出300個粒子而算出粒徑的標準偏差。將該等結果顯示在以下的表。The powder X-ray diffraction measurement was performed on the catalysts obtained in the above Examples and Comparative Examples, and the average particle diameter was calculated from the diffraction angle of the peaks and the half-value width thereof by the Scherrer's formula. Further, TEM observation (acceleration voltage: 200 KeV, magnification: 200,000 times) was performed, and 300 particles were selected from the five photographs taken to calculate the standard deviation of the particle diameter. These results are shown in the table below.
從表1來看，相較於實施例1，不使用靜力 混合器之比較例1及比較例2係平均粒徑大1至2nm左右。認為這是因為在實施例1，使反應系統在靜力混合器的反應管內之狹窄反應場內，而限制金還原步驟，而且使靜力混合器的葉片數適當化而使金粒子生成時的攪拌效率提升，藉此能夠謀求金粒子的小粒徑化。From Table 1, no static force is used compared to Example 1. In Comparative Example 1 and Comparative Example 2 of the mixer, the average particle diameter was about 1 to 2 nm. This is considered to be because, in the first embodiment, the reaction system is placed in a narrow reaction field in the reaction tube of the static mixer, and the gold reduction step is restricted, and the number of blades of the static mixer is appropriately adjusted so that the gold particles are generated. The stirring efficiency is improved, whereby the particle size of the gold particles can be reduced.
又，相較於實施例1，在比較例3係平均粒 徑為較粗大化之10nm左右。認為這是因為在金粒子未熟成完全的時候(被還原的金粒子係不穩定的時候)即擔持在碳上，金粒子在碳表面上凝聚且粗大化之緣故。因而，認為投入碳之時機較佳為在將A液與B液完全地混合結束後再添加。Further, in Comparative Example 3, the average particle was compared with Example 1. The diameter is about 10 nm which is coarser. This is considered to be because when the gold particles are not matured (when the gold particles to be reduced are unstable), they are supported on carbon, and the gold particles are aggregated and coarsened on the carbon surface. Therefore, it is considered that the timing of inputting carbon is preferably added after completely mixing the liquid A and the liquid B.
第1圖係實施例1所合成的金奈米粒子之 顯電子顯微鏡影像。金粒子係多半以2.5至5.0nm左右的狀態存在。又，對實施例1，藉由TEM觀察來測定粒徑分布時，係如第2圖所表示。從該結果來看，使用該製法所合成的金粒子係多半以2.5至5.0nm的狀態存在，作為核殼觸媒的核材，可說是在適當粒徑的範圍內。Figure 1 is a view of the gold nanoparticles synthesized in Example 1. SEM image. Most of the gold particles are present in a state of about 2.5 to 5.0 nm. Further, in Example 1, when the particle size distribution was measured by TEM observation, it is shown in Fig. 2 . From the results, most of the gold particles synthesized by the production method are present in a state of 2.5 to 5.0 nm, and the core material as a core-shell catalyst can be said to be in a range of an appropriate particle diameter.
[第二實施形態][Second embodiment]
在此，改變金鹽濃度、還原劑濃度、抗凝聚劑濃度而製造觸媒，且將所得到的觸媒的平均粒徑及標準偏差進行比較。Here, the catalyst was produced by changing the concentration of the gold salt, the concentration of the reducing agent, and the concentration of the anti-agglomerating agent, and the average particle diameter and standard deviation of the obtained catalyst were compared.
實施例2至5、比較例4Examples 2 to 5 and Comparative Example 4
調整氯金酸的添加量，調製含有濃度0.18至0.88mM的金鹽之A液。除了A液中的金濃度以外，B液的組成之條件係與實施例1相同。將結果顯示在以下的表。The amount of chloroauric acid added was adjusted to prepare a liquid A containing a gold salt having a concentration of 0.18 to 0.88 mM. The conditions of the composition of the liquid B were the same as those of the first embodiment except for the gold concentration in the liquid A. The results are shown in the table below.
從表2的結果來看，金濃度越高則金的平 均粒徑係變為越大。在比較例4，粒徑係成為6.1nm，而少許超過作為金核粒子之希望的平均粒徑範圍。因此，為了製造平均粒徑為3.0至5.0nm之作為核材之較佳金粒徑，係以實施例1至5的金濃度範圍為適合。From the results of Table 2, the higher the gold concentration, the higher the gold The average particle size ratio becomes larger. In Comparative Example 4, the particle size system was 6.1 nm, and slightly exceeded the desired average particle diameter range as the gold core particles. Therefore, in order to produce a preferred gold particle diameter as a core material having an average particle diameter of 3.0 to 5.0 nm, the gold concentration ranges of Examples 1 to 5 are suitable.
實施例6至9Examples 6 to 9
將在B液之氫化硼鈉(SBH)的添加量設為0.10至1.53g，調製含有濃度0.18至2.70mM的還原劑之B液。除了氫化硼鈉以外之條件，係與實施例1相同。將結果顯示在以下的表。The amount of sodium borohydride (SBH) added to the solution B was set to 0.10 to 1.53 g, and a liquid B containing a reducing agent having a concentration of 0.18 to 2.70 mM was prepared. The conditions other than sodium borohydride were the same as in Example 1. The results are shown in the table below.
從表3的結果來看，可知如實施例6，相對 於金濃度之SBH量變少時粒徑有變大之傾向。認為這是因為金粒子係以一部未還原的狀態存在，未還原粒子之間產生凝聚而粗大化。實際上，金的還原率係在實施例7至9為金投入量的98%以上，相對於此在實施例6為少許變低之95%。因此還原劑的投入量係以0.3mM以上為佳。From the results of Table 3, it can be seen that as in Example 6, the relative When the amount of SBH in the gold concentration is small, the particle size tends to become large. This is considered to be because the gold particles are present in a state in which they are not reduced, and aggregation occurs between the unreduced particles to be coarsened. In fact, the reduction ratio of gold was 98% or more of the amount of gold input in Examples 7 to 9, and was 95% which was slightly lower in Example 6 than this. Therefore, the amount of the reducing agent to be charged is preferably 0.3 mM or more.
實施例10至13Examples 10 to 13
調整抗凝聚劑之檸檬酸三鈉的添加量，調製相對於金鹽莫耳濃度為含有2至12倍的抗凝聚劑之A液。此外的條係與實施例1相同。又，在此，亦測定使碳擔體上擔持金粒子後進行抽吸過濾時，在濾液之金溶出量。該將結果顯示在下表。The amount of trisodium citrate added to the anti-agglomerating agent was adjusted to prepare a liquid A containing 2 to 12 times the anti-agglomerating agent with respect to the gold salt molar concentration. The other strips are the same as in the first embodiment. Here, the amount of gold eluted in the filtrate when the gold particles are supported on the carbon support and then subjected to suction filtration is also measured. The results are shown in the table below.
從表4的結果來看，能夠觀察到相對於金之檸檬酸鹽的投入量越多時，平均粒徑亦有變大之傾向。又，檸檬酸鹽的投入量變少時，在剛擔持後進行過濾時可觀察到金溶出至濾液。因此，為了製造3nm左右的粒子，實施例11的形態係可以說是最佳。From the results of Table 4, it can be observed that the larger the amount of the citrate added to gold, the larger the average particle diameter tends to be. Further, when the amount of the citrate input was small, it was observed that gold was eluted to the filtrate immediately after filtration. Therefore, in order to produce particles of about 3 nm, the morphology of Example 11 can be said to be optimal.
[第三實施形態][Third embodiment]
針對實施例1之擔持金之觸媒，實際上製成電極且測定氫氧化活性。測定用電極的製造及測定係依照以下的程序進行。又，作為比較對象，係製造比較例1之平均金粒徑為4.5nm的金/碳，相同地製造電極且進行評價。With respect to the catalyst for supporting gold of Example 1, an electrode was actually fabricated and the hydrogenation activity was measured. The production and measurement of the electrode for measurement were carried out in accordance with the following procedures. Further, as a comparison object, gold/carbon having an average gold particle diameter of 4.5 nm in Comparative Example 1 was produced, and an electrode was produced in the same manner and evaluated.
(電極製造)(electrode manufacturing)
在將離子交換樹脂(商品名：NAFION(註冊商標)、Dupont公司製)的5%溶液藉由噴霧乾燥所製成之1.2g樹脂粉末，以碳粉末基準稱量1g觸媒而混合，且將該等添加至25mL之1-丙醇與水的混合溶液，使用球磨機將其混合50分鐘而成為觸媒糊。然後，將在表層塗布有碳及離子交換樹脂之含浸PTFE而成之碳紙作為氣體擴散層，在此將前述觸媒糊以金量為0.56mg/cm2 的方式塗布印刷。而且，使其於60℃乾燥之後，於130℃、20kg/cm2 進行熱壓1分鐘而製成電極。1.2 g of a resin powder prepared by spray drying a 5% solution of an ion exchange resin (trade name: NAFION (registered trademark), manufactured by Dupont Co., Ltd.) was weighed and weighed by 1 g of a catalyst on a carbon powder basis, and These were added to 25 mL of a mixed solution of 1-propanol and water, and they were mixed for 50 minutes using a ball mill to become a catalyst paste. Then, carbon paper impregnated with PTFE coated with carbon and an ion exchange resin on the surface layer was used as a gas diffusion layer, and the catalyst paste was applied and printed so as to have a gold content of 0.56 mg/cm 2 . Further, after drying at 60 ° C, hot pressing was performed at 130 ° C and 20 kg / cm 2 for 1 minute to prepare an electrode.
(性能測定)(performance measurement)
係如以下方式測定上述所製成的電極之特性。使用所製成的電極而製造半電池(half cell)。在此，使用硫酸作為電解液且使用鉑網狀物作為相對極，而且使用標準氫電極 作為參考極，且將所製成的電極作為作用極而於其供給燃料而使電流流動，測定在電流密度500mA/cm2 之分極值(氫的氧化活性過電壓)。試驗條件係如以下。The characteristics of the electrode prepared above were measured in the following manner. A half cell was fabricated using the fabricated electrode. Here, sulfuric acid is used as the electrolyte and a platinum mesh is used as the opposite pole, and a standard hydrogen electrode is used as the reference electrode, and the electrode is used as a working electrode, and a current is supplied thereto to cause a current to flow, and the current is measured. The extreme value of the density of 500 mA/cm 2 (oxidation active overvoltage of hydrogen). The test conditions are as follows.
電極面積：7cm2 Electrode area: 7cm 2
溫度：60℃Temperature: 60 ° C
燃料：100%氫Fuel: 100% hydrogen
第3圖係氫氧化活性的測定結果。從該結果來看，相較於比較例1，實施例1係能夠達成高電流密度、低電壓。亦得知再相同的金擔持率時，因為金粒子越小則金屬表面積=氫氧化的反應場越寬闊，所以氫氧化活性高。如此能夠確認金粒子粒徑、粒徑分布之適當化對於活性改善係有效的，認為藉由在此種擔持金之觸媒擔持鉑，能夠得到有效的觸媒活性。Figure 3 is a measurement result of hydrogenation activity. From the results, in comparison with Comparative Example 1, Example 1 was able to achieve high current density and low voltage. When the same gold holding ratio is also known, the smaller the gold particles, the wider the reaction surface of the metal surface area = hydrogen hydroxide, so that the hydrogenation activity is high. In this way, it can be confirmed that the appropriateness of the particle size and the particle size distribution of the gold particles is effective for the activity improvement system, and it is considered that effective catalyst activity can be obtained by supporting platinum in such a catalyst for supporting gold.
根據本發明之擔持金之觸媒，能夠提供一種在減低鉑使用量之同時，能夠維持與只使用鉑之觸媒相同的觸媒性能之固體高分子型燃料電池用觸媒。According to the catalyst for supporting gold of the present invention, it is possible to provide a catalyst for a polymer electrolyte fuel cell capable of maintaining the same catalytic performance as that of a catalyst using only platinum while reducing the amount of platinum used.
本案代表圖無元件符號及其所代表之意義。This case represents a diagram without a component symbol and the meaning it represents.
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