JP5776102B2 - 白金原子の原子層を有する触媒を形成する方法 - Google Patents
白金原子の原子層を有する触媒を形成する方法 Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims description 88
- 238000000034 method Methods 0.000 title claims description 30
- 239000003054 catalyst Substances 0.000 title claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 24
- 229910052697 platinum Inorganic materials 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 150000003057 platinum Chemical class 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 238000006467 substitution reaction Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910000510 noble metal Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims 5
- 239000010410 layer Substances 0.000 description 17
- 239000004094 surface-active agent Substances 0.000 description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 9
- 238000004758 underpotential deposition Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000007771 core particle Substances 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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- B01J37/342—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 electric, magnetic or electromagnetic fields, e.g. for magnetic separation
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- 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
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- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
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- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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Description
白金単層触媒の調製
Pd/C粉末を、黒鉛シート上に直接、ゆるく配置するか、または、基体上に流し込み、加圧成形する。
Claims (13)
- 触媒材料を形成する方法であって、
白金クラスターの形成を制御するように置換反応の反応速度を抑制する、
ことを含み、白金の還元電位より低い還元電位を有する金属原子の原子層は、白金原子の原子層を備える触媒材料を製造するように、白金原子と置換され、前記の抑制することは、置換反応の反応速度を抑制するように、白金に配位する化合物を3.5mMまたはそれより高い濃度で含有する酸性溶液において、触媒材料を形成することを含むことを特徴とする、触媒材料を形成する方法。 - 金属原子は、銅を含むことを特徴とする請求項1記載の方法。
- 白金に配位する化合物は、クエン酸であることを特徴とする請求項1記載の方法。
- 白金に配位する化合物は、エチレンジアミン四酢酸(EDTA)であることを特徴とする請求項1記載の方法。
- 前記の抑制することは、白金に配位する化合物と、白金原子の少なくとも1つとの配位化合物を形成することを含むことを特徴とする請求項1記載の方法。
- 金属原子の原子層は、貴金属コア上にあることを特徴とする請求項1記載の方法。
- 触媒材料を形成する方法であって、
白金原子の原子層を備える触媒材料を製造するように、白金に配位する化合物を3.5mMまたはそれより高く含有する酸性溶液において、金属原子の原子層を白金原子と置換する、
ことを含み、金属原子は、白金の還元電位より低い還元電位を有することを特徴とする、触媒材料を形成する方法。 - 白金に配位する化合物は、クエン酸、EDTA、およびこれらの混合物から成る群より選択されることを特徴とする請求項7記載の方法。
- 酸性溶液は、さらに白金塩を含有することを特徴とする請求項7記載の方法。
- 触媒材料を形成する方法であって、
白金の還元電位より低い還元電位を有する金属原子の原子層で被覆された金属コアを備える粒子を提供し、
白金に配位する化合物および白金塩を含有する酸性溶液であって、白金に配位する化合物の濃度が3.5mMまたはそれより高い酸性溶液を提供し、
金属原子を溶液からの白金原子と置換して白金原子の原子層で被覆された金属コアを備える触媒材料を製造するように粒子を溶液で処理する、
ことを含むことを特徴とする、触媒材料を形成する方法。 - 電位下堆積(UPD)を用いて金属コア上に金属原子の原子層を堆積させることをさらに含むことを特徴とする請求項10記載の方法。
- 白金に配位する化合物は、クエン酸、EDTA、およびこれらの混合物から成る群より選択されることを特徴とする請求項10記載の方法。
- 粒子を溶液で処理することは、粒子を溶液と混合することを含むことを特徴とする請求項10記載の方法。
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PCT/US2011/025693 WO2012115624A1 (en) | 2011-02-22 | 2011-02-22 | Method of forming a catalyst with an atomic layer of platinum atoms |
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US (1) | US9610566B2 (ja) |
EP (1) | EP2678105B1 (ja) |
JP (1) | JP5776102B2 (ja) |
KR (1) | KR101568070B1 (ja) |
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JP6056963B2 (ja) * | 2013-04-18 | 2017-01-11 | トヨタ自動車株式会社 | 燃料電池用触媒及びその製造方法 |
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US8404613B2 (en) * | 2008-10-21 | 2013-03-26 | Brookhaven Science Associates, Llc | Platinum-based electrocatalysts synthesized by depositing contiguous adlayers on carbon nanostructures |
US8921260B2 (en) | 2010-02-12 | 2014-12-30 | Ballard Power Systems Inc. | Platinum monolayer on hollow, porous nanoparticles with high surface areas and method of making |
KR101793770B1 (ko) * | 2011-02-03 | 2017-11-03 | 아우디 아게 | 팔라듐계 코어 나노입자 상에 완전한 백금 단층을 제조하는 방법 |
EP2678105B1 (en) | 2011-02-22 | 2019-06-12 | Audi AG | Method of forming a catalyst with an atomic layer of platinum atoms |
CN103748719A (zh) | 2011-04-18 | 2014-04-23 | 联合工艺公司 | 形状受控的核壳型催化剂 |
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CN107649110A (zh) | 2018-02-02 |
US9610566B2 (en) | 2017-04-04 |
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CN103402631A (zh) | 2013-11-20 |
KR101568070B1 (ko) | 2015-11-10 |
US20130324394A1 (en) | 2013-12-05 |
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