JP2013252483A - 金担持カーボン触媒の製造方法 - Google Patents
金担持カーボン触媒の製造方法 Download PDFInfo
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- JP2013252483A JP2013252483A JP2012129429A JP2012129429A JP2013252483A JP 2013252483 A JP2013252483 A JP 2013252483A JP 2012129429 A JP2012129429 A JP 2012129429A JP 2012129429 A JP2012129429 A JP 2012129429A JP 2013252483 A JP2013252483 A JP 2013252483A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 115
- 239000010931 gold Substances 0.000 claims abstract description 114
- 229910052737 gold Inorganic materials 0.000 claims abstract description 114
- 239000002245 particle Substances 0.000 claims abstract description 114
- 239000007788 liquid Substances 0.000 claims abstract description 77
- 230000003068 static effect Effects 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 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 abstract 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 230000002776 aggregation Effects 0.000 claims description 12
- 238000004220 aggregation Methods 0.000 claims description 11
- 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
- 239000003112 inhibitor Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 5
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 229920002125 Sokalan® Polymers 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 3
- 239000003006 anti-agglomeration agent Substances 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 2
- 230000015271 coagulation Effects 0.000 abstract 2
- 238000005345 coagulation Methods 0.000 abstract 2
- 239000010938 white gold Substances 0.000 abstract 1
- 229910000832 white gold Inorganic materials 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 64
- 229910052697 platinum Inorganic materials 0.000 description 32
- 239000000446 fuel Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000012279 sodium borohydride Substances 0.000 description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 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
- 229920000642 polymer Polymers 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000002744 anti-aggregatory effect Effects 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000001509 sodium citrate Substances 0.000 description 5
- 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 5
- 229940038773 trisodium citrate Drugs 0.000 description 5
- 230000010718 Oxidation Activity Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000011162 core material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000011946 reduction process Methods 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002105 nanoparticle Substances 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 239000012670 alkaline solution Substances 0.000 description 2
- 229960004106 citric acid Drugs 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 150000001860 citric acid derivatives Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 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
- 239000010410 layer Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 238000001556 precipitation Methods 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
- 235000019263 trisodium citrate Nutrition 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 230000001133 acceleration Effects 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 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
- 238000011005 laboratory method Methods 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
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 230000010287 polarization Effects 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
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 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
- 238000001694 spray drying Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
【解決手段】担体であるカーボンに金粒子が担持された触媒において、金粒子は平均粒径2.0nm〜6.0nmであり、粒径の標準偏差が30%以内であることを特徴とする金担持カーボン触媒である。この金触媒は、金塩と凝集防止剤を含むA液と、還元剤と凝集防止剤を含むB液とを用意する工程と、調整したA液とB液とをスタティックミキサー中で反応させて金を還元させる工程と、金を還元させた後、A液とB液との混合液に担体であるカーボンを接触させて金を担持させる工程を含方法により製造される。
【選択図】図2
Description
(各混合液の調製)
純水5Lをケミカルミキサーで撹拌しながら金含有量48%の塩化金酸0.61gと、純度99%のクエン酸三ナトリウム2水和物2.5gとを添加し、塩化金塩0.29mM、クエン酸三ナトリウム1.70mM(0.05wt%)を含むA液を調整した。同様に、純水15Lを撹拌しながら純度92%の水素化ホウ素ナトリウム(SBH)0.51gと、純度99%のクエン酸三ナトリウム2水和物2.5gとを添加し、SBH0.83mM、クエン酸三ナトリウム0.57mM(0.02wt%)を含むB液を調整した。
調整したA液及びB液を、A液500mL/min、B液1000mL/minの流量として(A液:B液=1:2)、長さ13.5cm(エレメント数:20個)のスタティックミキサーにて混合して金を還元させた。混合液は20Lのホーロー製タンクで受け、タンク内の溶液は攪拌機(攪拌速度200rpm)により、攪拌を行った。尚、反応温度は25℃とした。混合後の溶液に、カーボン担体(ケッチェンブラックEC 比表面積800m2/g)0.43g添加して約3時間反応させ金粒子をカーボン担体上に担持させた。その後、吸引濾過を行い、純水ベッセル洗浄を3回行った後に60℃の大気圧乾燥機にて一昼乾燥させて金担持カーボン触媒を得た。
A液とB液を、スタティックミキサーを利用した反応系を使わず、ケミカルミキサー(攪拌速度800rpm)を用いて混合したことを除き、実施例1と同様の製造方法で触媒を製造した。
A液とB液を、スタティックミキサーを利用した反応系を使わず、ケミカルミキサー(攪拌速度300rpm)を用いて混合したことを除き、実施例1と同様の製造方法で触媒を製造した。
金の還元前にカーボン粉末を添加した。あらかじめA液とB液の混合液を受ける容器部分にコロイドミルを用いて高分散させたカーボン液添加してから、スタティックミキサーにてA液とB液と混合したこと以外、実施例1と同様の製造方法で触媒を製造した。
ここでは、金塩濃度、還元剤濃度、凝集防止剤濃度を変化させて触媒を製造し、得られた触媒の平均粒径及び標準偏差を比較した。
塩化金酸の添加量を調整し、濃度0.18〜0.88mMの金塩を含むA液を調製した。A液中の金濃度以外、及びB液の組成条件は、実施例1と同様とした。結果を以下の表に示す。
B液における水素化ホウ素ナトリウム(SBH)の添加量を0.10〜1.53gとして、濃度0.18〜2.70mMの還元剤を含むB液を調整した。水素化ホウ素ナトリウム以外の条件は、実施例1と同様とした。結果を以下の表に示す。
凝集防止剤であるクエン酸三ナトリウムの添加量を調整し、金塩モル濃度に対して2〜12倍の凝集防止剤を含むA液を調整した。それ以外の条件は、実施例1と同様とした。また、ここでは、金粒子をカーボン担体上に担持させた後の吸引濾過の際、濾液への金溶出量も測定した。この結果を以下の表に示す。
実施例1の金担持触媒について実際に電極を作成し水素酸化活性について測定をおこなった。測定用電極の作製および測定は以下の手順で行った。また、比較対象として、比較例1の平均金粒子径が4.5nmの金/カーボンを作成し、同様に電極を作成・評価した。
イオン交換樹脂(商品名:ナフィオン(登録商標)、Dupont社製)の5%溶液をスプレードライにより製造した樹脂粉末1.2gに触媒をカーボン粉末基準で1g秤量して混合し、これらを1−プロパノールと水との混合溶液25mLに入れ、これをボールミルにて50分間混合させて触媒ペーストとした。そして、カーボンとイオン交換樹脂とが表層にコーティングされたPTFEを含浸したカーボンペーパーをガス拡散層として、これに前記触媒ペーストを金量が0.56mg/cm2となるように塗布印刷した。更に、これを60℃で乾燥させた後、130℃、20kg/cm2で1分間ホットプレスして電極とした。
(性能測定)
上記で製作した電極の特性は、次のように測定した。作製した電極を用いて半電池(ハーフセル)を製造した。ここでは、硫酸を電解液とし、対極として白金メッシュを用い、参照極として標準水素電極を用い、作製した電極を作用極としてこれに燃料を供給して電流を流し、電流密度500mA/cm2における分極値(水素の酸化活性過電圧)を測定した。試験条件は以下の通りである。
電極面積:7cm2
温度:60℃
燃料:100%水素
Claims (6)
- 担体であるカーボンに金粒子が担持された触媒において、前記金粒子は、平均粒径2.0nm〜6.0nmであり、粒径の標準偏差が30%以内であることを特徴とする金担持カーボン触媒。
- 請求項1記載の金担持カーボン触媒の製造方法であって、
金塩と凝集防止剤を含むA液と、還元剤と凝集防止剤を含むB液とを用意する工程と、
調整したA液とB液とをスタティックミキサー中で反応させて金を還元させる工程と、
金を還元させた後、A液とB液との混合液に担体であるカーボンを接触させて金を担持させる工程を含む金担持カーボン触媒の製造方法。 - A液の金塩濃度は、0.10〜0.80mMであり、B液の還元剤濃度は、0.1〜5.0mMである請求項2記載の金担持カーボン触媒の製造方法。
- 凝集防止剤は、クエン酸、クエン酸塩、アスコルビン酸塩、ポリビニルピロリドン、ポリエチレンイミン、ポリアクリル酸、テトラメチルアンモニウムのいずれかである請求項2又は請求項3のいずれかに記載の金担持カーボン触媒の製造方法。
- A液中の凝集防止剤濃度は、金塩濃度に対してモル比で2〜15倍であり、B液中の凝集防止剤濃度は、還元剤濃度に対してモル比で0.2〜1.5倍である請求項2〜請求項4のいずれかに記載の金担持カーボン触媒の製造方法。
- 金を還元させる工程では、A液とB液とを1:1〜1:5の流量割合で混合させる請求項2〜5のいずれかに記載の金担持カーボン触媒の製造方法。
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