JP5754686B2 - Cathode platinum catalyst for highly active fuel cells - Google Patents
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims description 149
- 229910052697 platinum Inorganic materials 0.000 title claims description 73
- 239000003054 catalyst Substances 0.000 title claims description 49
- 239000000446 fuel Substances 0.000 title claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 85
- 229910052799 carbon Inorganic materials 0.000 claims description 79
- 230000000694 effects Effects 0.000 description 23
- 238000000034 method Methods 0.000 description 16
- 239000002245 particle Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 238000005259 measurement Methods 0.000 description 12
- 239000003273 ketjen black Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 150000003058 platinum compounds Chemical class 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000005518 polymer electrolyte Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- CTUFHBVSYAEMLM-UHFFFAOYSA-N acetic acid;platinum Chemical compound [Pt].CC(O)=O.CC(O)=O CTUFHBVSYAEMLM-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- -1 carbonyl quinone Chemical compound 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002848 electrochemical method Methods 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
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- HNKLPNDFOVJIFG-UHFFFAOYSA-N oxalic acid;platinum Chemical compound [Pt].OC(=O)C(O)=O HNKLPNDFOVJIFG-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- 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
本発明は低白金含有量でも高い活性を有する燃料電池用のカソード白金触媒に関する。 The present invention relates to a cathode platinum catalyst for fuel cells having high activity even with a low platinum content.
固体高分子型燃料電池は、クリーンで高いエネルギー変換効率を有することから、自動車用、家庭用、携帯用の電源としての利用が期待されている。 Since the polymer electrolyte fuel cell is clean and has high energy conversion efficiency, it is expected to be used as a power source for automobiles, homes, and portables.
この固体高分子形燃料電池には白金を主とした貴金属粒子をカーボン上に担持した触媒が用いられている。しかし、白金は高価であるため、担持した白金を有効活用し、電極触媒の活性を高める必要がある。そこで、触媒の活性を高めるために、合金化、白金粒子の微細化、高分散化などが提案されている。 In this polymer electrolyte fuel cell, a catalyst in which noble metal particles mainly composed of platinum are supported on carbon is used. However, since platinum is expensive, it is necessary to effectively use the supported platinum and increase the activity of the electrode catalyst. Therefore, in order to increase the activity of the catalyst, alloying, refinement of platinum particles, high dispersion, and the like have been proposed.
しかし、合金触媒は、白金重量当たりの活性は向上するが、白金の合金化に熱処理が必要であるため、白金粒子が成長し、結果的に低白金化が難しいという問題がある（特許文献１）。また、白金粒子の微粒子化及び高分散化は、単位白金重量当たりの活性点の数を増やすことができるが、粒子を小さくしすぎると白金の活性が低下することが報告されている（非特許文献１参照）。しかも、粒子サイズが小さくなると、白金粒子は酸化され易くなり、溶解再析出機構による白金触媒の劣化が進むことが知られている（非特許文献２参照）。 However, although the activity per platinum weight of the alloy catalyst is improved, since a heat treatment is required for alloying of platinum, there is a problem that platinum particles grow and as a result, it is difficult to reduce the platinum (Patent Document 1). ). In addition, fine particles and high dispersion of platinum particles can increase the number of active sites per unit platinum weight, but it has been reported that the activity of platinum decreases if the particles are made too small (non-patent). Reference 1). Moreover, it is known that when the particle size is reduced, the platinum particles are easily oxidized, and the platinum catalyst is deteriorated by the dissolution and reprecipitation mechanism (see Non-Patent Document 2).
本発明の目的は、燃料電池用のカソード白金触媒における白金の使用量を低減するために、白金の触媒特性を十分に引き出し、触媒の質的な活性を表す表面積あたりの活性（比活性）を向上させることである。 The object of the present invention is to sufficiently bring out the catalytic characteristics of platinum in order to reduce the amount of platinum used in the cathode platinum catalyst for fuel cells, and to obtain the activity per unit surface area (specific activity) representing the qualitative activity of the catalyst. It is to improve.
本発明者らは、上記の目的を達成すべく、白金をカーボン担体に担持させてなる白金担持カーボン触媒の特性につき鋭意検討を行った結果、今回、特定の光電子強度特性をもつカーボン担体に白金を担持させると、得られる白金担持カーボン触媒は、白金含有量が少なくても、非常に高い触媒活性を発揮することを見出し、本発明を完成するに至った。 In order to achieve the above-mentioned object, the present inventors have conducted intensive studies on the characteristics of a platinum-supported carbon catalyst in which platinum is supported on a carbon support. As a result, this time, platinum is applied to a carbon support having specific photoelectron intensity characteristics. As a result, it was found that the platinum-supported carbon catalyst obtained exhibited a very high catalytic activity even when the platinum content was small, and the present invention was completed.
かくして、本発明は、白金をカーボン担体に担持させてなる白金担持カーボン触媒であって、Ｘ線光電子分光装置（ＸＰＳ）で測定される、カーボン担体のｓｐ２混成軌道とｓｐ３混成軌道の光電子強度の積分強度比ｓｐ２／ｓｐ３が１．８〜３．３の範囲内にある白金担持カーボン触媒を提供するものである。 Thus, the present invention is a platinum-supported carbon catalyst in which platinum is supported on a carbon support, and the photoelectrons of the sp 2 hybrid orbital and sp 3 hybrid orbit of the carbon support measured by an X-ray photoelectron spectrometer (XPS). A platinum-supported carbon catalyst having an integrated intensity ratio sp 2 / sp 3 in the range of 1.8 to 3.3 is provided.
本発明の白金担持カーボン触媒は、白金含有量が少なくても、非常に高い触媒活性を有しており、例えば、通常の白金担持カーボン触媒と比較して、１．３倍以上という高い比活性を有する。 The platinum-supported carbon catalyst of the present invention has a very high catalytic activity even when the platinum content is small, for example, a specific activity that is 1.3 times or more higher than that of a normal platinum-supported carbon catalyst. Have
本発明の白金担持カーボン触媒は、径が２〜５ｎｍの範囲内にある白金粒子がカーボン担体上に分散・担持された構造を有する。かかる白金担持カーボン触媒においては、白金粒子は分子間力によってカーボン担体上に吸着していると言われている。本発明者らは、活性点を有する白金粒子の活性が、白金が吸着しているカーボン担体の電子状態によって変化することを発見し、カーボン担体の電子状態を変化させることにより、通常の白金担持カーボン触媒と比較して１．３倍以上という高い比活性を有する白金担持カーボン触媒を提供することに成功した。 The platinum-supported carbon catalyst of the present invention has a structure in which platinum particles having a diameter in the range of 2 to 5 nm are dispersed and supported on a carbon support. In such a platinum-supported carbon catalyst, the platinum particles are said to be adsorbed on the carbon support by intermolecular force. The present inventors discovered that the activity of platinum particles having an active site changes depending on the electronic state of the carbon carrier on which platinum is adsorbed, and by changing the electronic state of the carbon carrier, The present inventors have succeeded in providing a platinum-supported carbon catalyst having a high specific activity of 1.3 times or more compared with a carbon catalyst.
カーボン担体の電子状態は、Ｘ線光電子分光装置（ＸＰＳ）によって測定されるＣ１ｓスペクトルのｓｐ２混成軌道とｓｐ３混成軌道の光電子強度の積分強度比（面積比）（ｓｐ２／ｓｐ３）から求めることができ、本発明の白金担持カーボン触媒は、該積分強度比（ｓｐ２／ｓｐ３）が１．８〜３．３、好ましくは１．９〜３．２、さらに好ましくは２．１〜３．１の範囲内にあることができる。 The electronic state of the carbon support is determined from the integrated intensity ratio (area ratio) (sp 2 / sp 3 ) of the photoelectron intensity of the sp 2 hybrid orbit of the C1s spectrum and the sp 3 hybrid orbit measured by an X-ray photoelectron spectrometer (XPS) In the platinum-supported carbon catalyst of the present invention, the integrated intensity ratio (sp 2 / sp 3 ) is 1.8 to 3.3, preferably 1.9 to 3.2, more preferably 2.1. It can be in the range of ~ 3.1.
本発明において使用しうるカーボン担体としては、例えば、導電性カーボンとして市販されているもののほか、活性炭、グラファイト、カーボンナノチューブ、カーボンナノホーン、フラーレン等が挙げられる。 Examples of the carbon support that can be used in the present invention include activated carbon, graphite, carbon nanotubes, carbon nanohorns, fullerenes and the like in addition to those commercially available as conductive carbon.
カーボン担体の電子状態は、熱処理によって変化させることができる。該熱処理は、例えば、真空又は不活性ガス雰囲気中にて、通常１０００〜１８００℃、好ましくは１２００〜１５００℃の温度で加熱することにより行うことができ、熱処理条件を変えて操作することにより、カーボンの消耗を抑制しつつ、電子状態の異なるカーボン担体を得ることができる。 The electronic state of the carbon support can be changed by heat treatment. The heat treatment can be performed, for example, by heating at a temperature of usually 1000 to 1800 ° C., preferably 1200 to 1500 ° C. in a vacuum or an inert gas atmosphere. By operating by changing the heat treatment conditions, It is possible to obtain carbon carriers having different electronic states while suppressing carbon consumption.
前記不活性ガスとしては、例えば、窒素、アルゴン、ヘリウム等を用いることができ、なかでもアルゴンが適している。 As said inert gas, nitrogen, argon, helium etc. can be used, for example, Argon is especially suitable.
ＸＰＳによって測定されるＣ１ｓスペクトルのｓｐ２混成軌道とｓｐ３混成軌道の光電子強度の積分強度比（面積比）（ｓｐ２／ｓｐ３）が１．８〜３．３の範囲内にあるカーボン担体は、上記熱処理の温度及び時間を調節することにより、経験的に得ることができる。 Carbon support in which the integrated intensity ratio (area ratio) (sp 2 / sp 3 ) of the photoelectron intensity of the sp 2 hybrid orbit and sp 3 hybrid orbit of the C1s spectrum measured by XPS is in the range of 1.8 to 3.3 Can be obtained empirically by adjusting the temperature and time of the heat treatment.
かくして得られるカーボン担体への白金粒子の担持方法は、特に限定されるものではなく、それ自体既知の各種方法を用いることができるが、一般には、白金化合物をカーボン担体上に担持させた状態で、その白金化合物を還元してカーボン担体上に白金粒子を析出させる方法が好適である。該白金化合物としては、例えば、塩化白金、酸化白金、硝酸白金、ジニトロジアミン白金、酢酸白金、シュウ酸白金等が挙げられ、なかでも塩素を含まない化合物が適している。白金粒子をカーボン担体上に担持させる方法としては、具体的に、例えば、含浸法に従い、上記の如き白金化合物の溶液をカーボン担体に含浸させ、場合により乾燥した後、担持された白金化合物を還元する方法が挙げられる。その際の還元は、例えば、熱分解による還元方法、水素や一酸化炭素による気体の還元剤による還元方法、エタノール、メタノール、ヒドラジン、水素化ホウ素ナトリウムのような液体の還元剤による還元方法により行うことができる。また、液相還元法を使用することにより、カーボン担体への白金化合物の担持と還元を同時的に行うこともでき、それにより白金担持カーボン触媒を得ることができる。該液相還元法は、具体的には、例えば、カーボン担体にジニトロジアンミンＰｔエタノール溶液、クエン酸及びエタノールを添加し、加熱還流することにより行うことができる。 The method for supporting the platinum particles on the carbon carrier thus obtained is not particularly limited, and various methods known per se can be used, but in general, the platinum compound is supported on the carbon carrier. A method of reducing the platinum compound and precipitating platinum particles on the carbon support is preferable. Examples of the platinum compound include platinum chloride, platinum oxide, platinum nitrate, dinitrodiamine platinum, platinum acetate, platinum oxalate and the like, and among them, a compound containing no chlorine is suitable. Specifically, the platinum particles are supported on the carbon support by, for example, impregnating the platinum support as described above in accordance with the impregnation method, and optionally drying the supported platinum compound after reduction. The method of doing is mentioned. In this case, the reduction is performed by, for example, a reduction method using thermal decomposition, a reduction method using a gaseous reducing agent such as hydrogen or carbon monoxide, or a reduction method using a liquid reducing agent such as ethanol, methanol, hydrazine, or sodium borohydride. be able to. Further, by using the liquid phase reduction method, it is possible to simultaneously support and reduce the platinum compound on the carbon carrier, thereby obtaining a platinum-supported carbon catalyst. Specifically, the liquid phase reduction method can be performed, for example, by adding a dinitrodiammine Pt ethanol solution, citric acid and ethanol to a carbon support and heating to reflux.
本発明の白金担持カーボン触媒における白金の担持量は、触媒の重量を基準にして、一般に１０〜７０重量％、特に２０〜６０重量％、さらに特に３０〜５０重量％の範囲内であることが好ましい。 The supported amount of platinum in the platinum-supported carbon catalyst of the present invention is generally in the range of 10 to 70% by weight, particularly 20 to 60% by weight, more particularly 30 to 50% by weight, based on the weight of the catalyst. preferable.
本発明の白金担持カーボン触媒の酸素還元特性は、回転電極法にて測定することにより、１．０５Ｖから０．０５Ｖまで走査した時の０．８５Ｖでの電流値から求めることができる。そのときの測定条件としては、電解質：０．５Ｍ−硫酸水溶液、測定温度：６０℃、回転電極の回転速度：２０００ｒｐｍを採用することができる。測定される結果から、図１に示すグラフが得られる。 The oxygen reduction characteristics of the platinum-supported carbon catalyst of the present invention can be determined from the current value at 0.85 V when scanning from 1.05 V to 0.05 V by measuring by the rotating electrode method. As measurement conditions at that time, electrolyte: 0.5 M-sulfuric acid aqueous solution, measurement temperature: 60 ° C., rotation speed of the rotating electrode: 2000 rpm can be employed. The graph shown in FIG. 1 is obtained from the measured result.
市販されている通常の白金担持触媒の比活性は０．１３Ａ／ｍ２であるが、ｓｐ２混成軌道とｓｐ３混成軌道の積分強度比（ｓｐ２／ｓｐ３）が１．８〜３．３の範囲内にあるカーボン担体を用いた本発明の白金担持カーボン触媒の比活性は０．１７Ａ／ｍ２以上であって、通常の白金担持触媒の比活性の１．３倍以上という高い触媒活性を有する。 The specific activity of a commercially available platinum-supported catalyst is 0.13 A / m 2 , but the integrated intensity ratio (sp 2 / sp 3 ) between the sp 2 hybrid orbitals and sp 3 hybrid orbitals is 1.8-3. The specific activity of the platinum-supported carbon catalyst of the present invention using the carbon support in the range of 3 is 0.17 A / m 2 or more, and is a catalyst having a high specific activity of 1.3 times or more of the specific activity of the usual platinum-supported catalyst. Has activity.
以下、実施例および比較例により本発明をさらに具体的に説明するが、これらの実施例により本発明の範囲は何ら制限されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, the scope of the present invention is not restrict | limited at all by these Examples.
実施例１
ケッチェンブラックＥＣ３００Ｊ（導電性カーボン、ケッチェン・ブラック・インターナショナル株式会社社製、商品名）をアルゴン雰囲気中にて１５００℃で熱処理し、熱処理カーボン：ＫＢＥＣ３００Ｊ−１５００を得た。このＫＢＥＣ３００Ｊ−１５００を０．６ｇ、ジニトロジアンミンＰｔエタノール溶液をＰｔ換算で０．４ｇ、クエン酸を２．０ｇ及びエタノールを１００ｇ還流装置に仕込み混合し、１６時間還流還元することにより、触媒重量を基準にして４０重量％の白金が担持された白金担持カーボン触媒：４０ｗｔ％Ｐｔ／ＫＢＥＣ３００Ｊ−１５００を得た。
Example 1
Ketjen Black EC300J (conductive carbon, manufactured by Ketjen Black International Co., Ltd., trade name) was heat treated at 1500 ° C. in an argon atmosphere to obtain heat treated carbon: KBEC300J-1500. This KBEC300J-1500 is 0.6 g, dinitrodiammine Pt ethanol solution is 0.4 g in terms of Pt, citric acid is 2.0 g, and ethanol is 100 g. The mixture is refluxed for 16 hours to reduce the catalyst weight. A platinum-supported carbon catalyst on which 40% by weight of platinum was supported on the basis was obtained: 40 wt% Pt / KBEC300J-1500.
実施例２
ケッチェンブラックＥＣ３００Ｊ（導電性カーボン、ケッチェン・ブラック・インターナショナル社製、商品名）をアルゴン雰囲気中にて１８００℃で熱処理し、熱処理カーボン：ＫＢＥＣ３００Ｊ−１８００を得た。このＫＢＥＣ３００Ｊ−１８００を実施例１と同様に処理して、触媒重量を基準にして４０重量％の白金が担持された白金担持カーボン触媒：４０ｗｔ％Ｐｔ／ＫＢＥＣ３００Ｊ−１８００を得た。
Example 2
Ketjen Black EC300J (conductive carbon, manufactured by Ketjen Black International Co., Ltd., trade name) was heat treated at 1800 ° C. in an argon atmosphere to obtain heat treated carbon: KBEC300J-1800. This KBEC300J-1800 was treated in the same manner as in Example 1 to obtain a platinum-supported carbon catalyst on which 40% by weight of platinum was supported based on the catalyst weight: 40 wt% Pt / KBEC300J-1800.
実施例３
ケッチェンブラックＥＣ６００ＪＤを真空雰囲気中にて１０００℃で熱処理し、熱処理カーボン：ＫＢＥＣ６００ＪＤ−１０００を得た。このＫＢＥＣ６００ＪＤ−１０００を実施例１と同様に処理して、４０重量％の白金が担持された白金担持カーボン触媒：４０ｗｔ％Ｐｔ／ＫＢＥＣ６００ＪＤ−１０００を得た。
Example 3
Ketjen black EC600JD was heat-treated at 1000 ° C. in a vacuum atmosphere to obtain heat-treated carbon: KBEC600JD-1000. This KBEC600JD-1000 was treated in the same manner as in Example 1 to obtain a platinum-supported carbon catalyst on which 40% by weight of platinum was supported: 40 wt% Pt / KBEC600JD-1000.
実施例４
ケッチェンブラックＥＣ６００ＪＤをアルゴン雰囲気中にて１５００℃で熱処理し、熱処理カーボン：ＫＢＥＣ６００ＪＤ−１５００を得た。このＫＢＥＣ６００ＪＤ−１５００に実施例１と同様に処理して、４０重量％の白金が担持された白金担持カーボン触媒：４０ｗｔ％Ｐｔ／ＫＢＥＣ６００ＪＤ−１５００を得た。
Example 4
Ketjen black EC600JD was heat-treated at 1500 ° C. in an argon atmosphere to obtain heat-treated carbon: KBEC600JD-1500. This KBEC600JD-1500 was treated in the same manner as in Example 1 to obtain a platinum-supported carbon catalyst on which 40% by weight of platinum was supported: 40 wt% Pt / KBEC600JD-1500.
比較例１
熱処理していないケッチェンブラックＥＣ３００Ｊを実施例１と同様に処理して、４０重量％の白金が担持された白金担持カーボン触媒：４０ｗｔ％Ｐｔ／ＫＢＥＣ３００Ｊを得た。
Comparative Example 1
Untreated Ketjen Black EC300J was treated in the same manner as in Example 1 to obtain a platinum-supported carbon catalyst on which 40% by weight of platinum was supported: 40 wt% Pt / KBEC300J.
比較例２
ケッチェンブラックＥＣ３００Ｊを１０００℃、真空雰囲気で熱処理し、熱処理カーボン：ＫＢＥＣ３００Ｊ−１０００を得た。このＫＢＥＣ３００Ｊ−１０００に実施例１と同様に処理して、４０重量％の白金が担持された白金担持カーボン触媒：４０ｗｔ％Ｐｔ／ＫＢＥＣ３００ＪＤ−１０００を得た。
Comparative Example 2
Ketjen black EC300J was heat-treated at 1000 ° C. in a vacuum atmosphere to obtain heat-treated carbon: KBEC300J-1000. This KBEC300J-1000 was treated in the same manner as in Example 1 to obtain a platinum-supported carbon catalyst on which 40% by weight of platinum was supported: 40 wt% Pt / KBEC300JD-1000.
比較例３
ケッチェンブラックＥＣ３００Ｊを真空雰囲気中にて１２００℃で熱処理し、熱処理カーボン：ＫＢＥＣ３００Ｊ−１２００を得た。このＫＢＥＣ３００Ｊ−１２００に実施例１と同様に処理して、４０重量％の白金が担持された白金担持カーボン触媒：４０ｗｔ％Ｐｔ／ＫＢＥＣ３００Ｊ−１２００を得た。
Comparative Example 3
Ketjen Black EC300J was heat-treated at 1200 ° C. in a vacuum atmosphere to obtain heat-treated carbon: KBEC300J-1200. This KBEC300J-1200 was treated in the same manner as in Example 1 to obtain a platinum-supported carbon catalyst on which 40% by weight of platinum was supported: 40 wt% Pt / KBEC300J-1200.
比較例４
ケッチェンブラックＥＣ３００Ｊをアルゴン雰囲気中にて２０００℃で熱処理し、熱処理カーボン：ＫＢＥＣ３００Ｊ−２０００を得た。このＫＢＥＣ３００Ｊ−２０００に実施例１と同様に処理して、４０重量％の白金が担持された白金担持カーボン触媒：４０ｗｔ％Ｐｔ／ＫＢＥＣ３００Ｊ−２０００を得た。
Comparative Example 4
Ketjen Black EC300J was heat-treated at 2000 ° C. in an argon atmosphere to obtain heat-treated carbon: KBEC300J-2000. This KBEC300J-2000 was treated in the same manner as in Example 1 to obtain a platinum-supported carbon catalyst on which 40% by weight of platinum was supported: 40 wt% Pt / KBEC300J-2000.
比較例５
熱処理をしていないケッチェンブラックＥＣ６００ＪＤに実施例１と同様にして、４０重量％の白金が担持された白金担持カーボン触媒：４０ｗｔ％Ｐｔ／ＫＢＥＣ６００ＪＤを得た。
Comparative Example 5
In the same manner as in Example 1, platinum-supported carbon catalyst in which 40 wt% platinum was supported: 40 wt% Pt / KBEC 600 JD was obtained.
比較例６
ケッチェンブラックＥＣ６００ＪＤをアルゴン雰囲気中にて２０００℃で熱処理し、熱処理カーボン：ＫＢＥＣ６００ＪＤ−２０００を得た。このＫＢＥＣ６００ＪＤ−２０００に実施例１と同様に処理して、４０重量％の白金が担持された白金担持カーボン触媒：４０ｗｔ％Ｐｔ／ＫＢＥＣ６００ＪＤ−２０００を得た。
Comparative Example 6
Ketjen black EC600JD was heat-treated at 2000 ° C. in an argon atmosphere to obtain heat-treated carbon: KBEC600JD-2000. This KBEC600JD-2000 was treated in the same manner as in Example 1 to obtain a platinum-supported carbon catalyst on which 40% by weight of platinum was supported: 40 wt% Pt / KBEC600JD-2000.
上記実施例１〜４及び比較例１〜６で得られたカーボン担体のｓｐ２混成軌道とｓｐ３混成軌道の光電子強度の積分強度比ならびに白金担持カーボン触媒の白金粒子径、白金の比表面積及び比活性は以下の方法で測定した。 The integrated intensity ratio of the photoelectron intensities of the sp 2 hybrid orbitals and sp 3 hybrid orbitals of the carbon supports obtained in Examples 1 to 4 and Comparative Examples 1 to 6, the platinum particle diameter of the platinum-supported carbon catalyst, the specific surface area of platinum, and Specific activity was measured by the following method.
Ｃ１ｓ Ｘ線光電子分光（ＸＰＳ）測定で得られたスペクトルに対し、下記の解析を行うことで決定した。測定には、ＫＲＡＴＯＳ社製ＡＸＩＳ−ＮＯＶＡを使用し、Ｘ線源としてＡｌ Ｋα線（印加電圧１５ｋＶ、エミッション電流１０ｍＡ）を用い、高エネルギー分解条件で、試料を導電性カーボンテープ上に固定して測定を行った。なお、帯電補正はＣ１ｓのピークトップを２８４．５ｅＶとすることにより行った。 It determined by performing the following analysis with respect to the spectrum obtained by C1s X-ray photoelectron spectroscopy (XPS) measurement. For measurement, AXIS-NOVA manufactured by KRATOS was used, Al Kα ray (applied voltage 15 kV, emission current 10 mA) was used as an X-ray source, and the sample was fixed on a conductive carbon tape under high energy decomposition conditions. Measurements were made. The charge correction was performed by setting the C1s peak top to 284.5 eV.
Ｃ１ｓスペクトルは５種類の状態（ｓｐ３混成軌道炭素：ピーク位置２８４．５４３±０．１０６ｅＶ、ｓｐ２混成軌道炭素：ピーク位置２８５．０５１±０．０９６ｅＶ、フェノール・アルコール型炭素：ピーク位置２８５．７６６±０．０８３ｅＶ、カルボニル・キノン型炭素：ピーク位置２８６．８９２±０．０８９ｅＶ、カルボキシル型炭素：ピーク位置２８９．３０５±０．１６７ｅＶ）をとり得るため、それぞれの状態にピーク分離を行った。ピーク分離は、ピーク位置を固定したガウス−ローレンツ混合関数の線形結合により、スペクトルを近似することにより行った。 The C1s spectrum has five states (sp 3 hybrid orbital carbon: peak position 284.543 ± 0.106 eV, sp 2 hybrid orbital carbon: peak position 285.051 ± 0.096 eV, phenol / alcohol type carbon: peak position 285. 766 ± 0.083 eV, carbonyl quinone type carbon: peak position 286.892 ± 0.089 eV, carboxyl type carbon: peak position 289.305 ± 0.167 eV), and peak separation was performed in each state. . Peak separation was performed by approximating the spectrum by linear combination of Gauss-Lorentz mixing functions with fixed peak positions.
白金の粒子径の測定には、リガク社製、ＲＩＮＴ Ｕｌｔｉｍａ ＩＩＩを用い、Ｘ線回折測定を行い、得られた回折パターンからＰｔの２２０回折線の半価幅に下記のシェラーの式を適用することにより結晶子径を算出した。
Ｄ＝Ｋ・λ／βｃｏｓθ
Ｄ：結晶子径
λ：測定Ｘ線波長
β：半価幅
θ：回折線のブラッグ角
Ｋ：シェラー定数＝０．９
For the measurement of the particle diameter of platinum, X-ray diffraction measurement is performed using RINT Ultimate III manufactured by Rigaku Corporation, and the following Scherrer equation is applied to the half-value width of 220 diffraction lines of Pt from the obtained diffraction pattern. Thus, the crystallite diameter was calculated.
D = K · λ / βcos θ
D: Crystallite diameter λ: Measurement X-ray wavelength β: Half width θ: Bragg angle of diffraction line K: Scherrer constant = 0.9
白金の比表面積は、大倉理研社製Ｒ６０１５を用いて以下の手順で測定した。白金担持カーボンを０．１５ｇ採取し、水素雰囲気、１３０℃の条件で前処理し、前処理後、測定系内に一酸化炭素をパルス法にて導入し、３６０秒間保持する操作を一酸化炭素が白金表面上に飽和吸着に達するまで繰り返す。その際、一酸化炭素の導入量と排出量の差が３回連続±２％以下になった場合に飽和吸着に達したと判定した。一酸化炭素の白金表面への吸着量を導入量と排出量の差から算出し、その一酸化炭素吸着量から白金比表面積を以下の式にしたがって算出した。
ａＰｔ＝（ＶＣＯ×ＮＡ×ｎＰｔ×１０−１８×１００）／（２２４１４×ｋｓｆ×ｃ）
ａＰｔ：白金比表面積（ｍ２・ｇ−１）
ＶＣＯ：一酸化炭素の吸着量（ｍｌ）
ＮＡ：アボガドロ定数＝６．０２２×１０２３
ｎＰｔ：白金１原子が占める断面積＝０．０８ｎｍ２・ａｔｏｍ−１
ｋｓｆ：化学両論比（白金原子１個と反応するガス分子の個数）＝１
The specific surface area of platinum was measured by the following procedure using R6015 manufactured by Okura Riken. 0.15 g of platinum-supported carbon was sampled, pretreated under conditions of hydrogen atmosphere and 130 ° C., and after pretreatment, carbon monoxide was introduced into the measurement system by a pulse method and held for 360 seconds. Repeat until saturated adsorption is reached on the platinum surface. At that time, it was determined that saturated adsorption was reached when the difference between the amount of carbon monoxide introduced and the amount of discharge was continuously ± 2% or less three times. The adsorption amount of carbon monoxide on the platinum surface was calculated from the difference between the introduction amount and the discharge amount, and the platinum specific surface area was calculated from the carbon monoxide adsorption amount according to the following formula.
a Pt = (V CO × N A × n Pt × 10 -18 × 100) / (22414 × k sf × c)
a Pt : Platinum specific surface area (m 2 · g −1 )
V CO : Adsorption amount of carbon monoxide (ml)
N A : Avogadro constant = 6.022 × 10 23
n Pt : Cross-sectional area occupied by one platinum atom = 0.08 nm 2 · atom -1
k sf : stoichiometric ratio (number of gas molecules reacting with one platinum atom) = 1
白金担持カーボンの比活性は以下のようにして測定した：試験電極は一般的にＳｃｈｍｉｄｔ法（Ｕ．Ａ．Ｐａｕｌｕｓ ｅｔ．ａｌ．，Ｊｏｕｒｎａｌ ｏｆ Ｅｌｅｃｔｒｏａｎａｌｙｔｉｃａｌ Ｃｈｅｍｉｓｔｒｙ ４９５（２００１）１３４-１４５）と呼ばれる方法により作製した。Ｐｔ／Ｃを１０ｍｇ採取し、窒素雰囲気下でエタノール１０ｍｌに浸漬する。これに超音波で３０ｍｉｎかけて、Ｐｔ／Ｃを分散させてＰｔ／Ｃ分散溶液を作製した。回転電極のグラシーカーボン上にＰｔ／Ｃ分散溶液を１０μｌ採取し、室温にて乾燥させる。メタノール（ＭｅＯＨ）で１５０倍に希釈したＮａｆｉｏｎ（登録商標）溶液（３０ｗｔ％、アルドリッチ製）を塗布して、室温乾燥、８０℃の乾燥機で乾燥サイクルを２回繰り返す。電解質溶液は０．５Ｍの硫酸水溶液、測定温度は６０℃、参照電極はＡｇ／ＡｇＣｌとした。電極の電気化学的な酸化還元による前処理条件は０．０５Ｖ〜１．２Ｖ、５０ｍＶ／ｓｅｃ、Ｏ２雰囲気とし、水素吸着によるＰｔ表面積（ＥＣＳＡ）の測定条件は０．０５Ｖ〜１．２Ｖ、５ｍＶ／ｓｅｃ、Ｎ２雰囲気とし、酸素還元活性の測定条件は１．０５Ｖ→０．０５Ｖ、５ｍＶ／ｓｅｃ、Ｎ２雰囲気、２０００ｒｐｍとした。なお、ＥＣＳＡ測定には、標準的に用いられている担持白金触媒の持つ水素吸着に関わる電気量（２１０μＣ・ｃｍ−２）を用いた。 The specific activity of the platinum-supported carbon was measured as follows: The test electrode was generally measured by a method called Schmidt method (UA Paulus et. Al., Journal of Electrochemical Chemistry 495 (2001) 134-145). Produced. 10 mg of Pt / C is collected and immersed in 10 ml of ethanol under a nitrogen atmosphere. A Pt / C dispersion solution was prepared by dispersing Pt / C with ultrasonic waves for 30 minutes. 10 μl of Pt / C dispersion is collected on the glassy carbon of the rotating electrode and dried at room temperature. A Nafion (registered trademark) solution (30 wt%, manufactured by Aldrich) diluted 150-fold with methanol (MeOH) is applied, and the drying cycle is repeated twice in a dryer at room temperature and 80 ° C. The electrolyte solution was a 0.5 M sulfuric acid aqueous solution, the measurement temperature was 60 ° C., and the reference electrode was Ag / AgCl. The pretreatment conditions by electrochemical oxidation-reduction of the electrodes are 0.05 V to 1.2 V, 50 mV / sec, an O 2 atmosphere, and the measurement conditions of the Pt surface area (ECSA) by hydrogen adsorption are 0.05 V to 1.2 V, 5 mV / sec, and N 2 atmosphere, measurement conditions of the oxygen reduction activity was 1.05V → 0.05V, 5mV / sec, N 2 atmosphere, and 2000 rpm. For the ECSA measurement, the quantity of electricity (210 μC · cm −2 ) related to hydrogen adsorption of a supported platinum catalyst used as a standard was used.
その結果を下記表１に示す。 The results are shown in Table 1 below.
図１は、表１に示した比活性を光電子強度の積分強度比（ｓｐ２／ｓｐ３）に対してプロットしたものであり、異なる炭素担体上に担持された白金触媒の示す酸素還元活性は、担体カーボンの有するｓｐ２／ｓｐ３混成軌道の比に大きく支配されていることを示す。ｓｐ２混成軌道はグラファイトに代表されるカーボン材料に含まれる炭素原子に代表的な結合形態である。これに対して、ｓｐ３混成軌道はダイヤモンドや脂肪族炭化水素に含まれる炭素原子に代表的な結合形態である。前者はπ電子を含むため高い導電性をもたらす。これに対して、後者はそのような電子を含まないため導電性は低い。ｓｐ２／ｓｐ３強度比が高くなるということは、カーボン材料の導電性が高いことを意味する。 FIG. 1 is a plot of the specific activities shown in Table 1 against the integrated intensity ratio of photoelectron intensity (sp 2 / sp 3 ), and the oxygen reduction activity exhibited by platinum catalysts supported on different carbon supports is This shows that it is largely governed by the ratio of sp 2 / sp 3 hybrid orbital possessed by the carrier carbon. The sp 2 hybrid orbital is a bonding form typical of carbon atoms contained in a carbon material typified by graphite. On the other hand, sp 3 hybrid orbitals are a typical bonding form for carbon atoms contained in diamond and aliphatic hydrocarbons. The former brings high conductivity because it contains π electrons. On the other hand, since the latter does not contain such electrons, the conductivity is low. An increase in the sp 2 / sp 3 intensity ratio means that the carbon material has high conductivity.
本触媒は、電気化学反応を促進するものであるから、担体には高い導電性が求められる。このことが強く反映されているのが、ｓｐ２／ｓｐ３比が２．８（実施例１）までの傾向である。さらに、ｓｐ２／ｓｐ３比が増加することにより、カーボン表面には、グラファイト構造のベーサル面が多く形成されることが予測される。このようなカーボン表面は、その上に担持される白金の分散状態および電子状態に影響を及ぼす可能性がある。まず、分散性であるが、ｓｐ２／ｓｐ３強度比と白金粒子径もしくは比表面積の間には相関はない。このことより、ｓｐ２／ｓｐ３比が分散性を変化させ、それにより比活性が低下するという仮説は棄却される。次に、電子状態であるが、白金の電子状態をＸＰＳ Ｐｔ４ｆスペクトルにより検討した結果、高い活性を示す触媒の白金は還元状態にあることが見いだされている。これは、カーボン表面の炭素原子の結合状態が白金の電子状態に影響を及ぼす、いわゆる金属−担体相互作用の発現である。ｓｐ２混成炭素原子の発達はこのような状態の白金を示さなくなると仮定することにより、ｓｐ２／ｓｐ３＞２．８領域における比活性の低下を説明することができる。 Since this catalyst promotes an electrochemical reaction, the support is required to have high conductivity. This is strongly reflected in the tendency for the sp 2 / sp 3 ratio to reach 2.8 (Example 1). Furthermore, it is predicted that a large number of basal surfaces having a graphite structure are formed on the carbon surface by increasing the sp 2 / sp 3 ratio. Such a carbon surface can affect the dispersion and electronic state of platinum supported thereon. First, with respect to dispersibility, there is no correlation between the sp 2 / sp 3 intensity ratio and the platinum particle diameter or specific surface area. This rejects the hypothesis that the sp 2 / sp 3 ratio changes dispersibility and thereby reduces specific activity. Next, as a result of examining the electronic state of platinum by XPS Pt4f spectrum, it has been found that platinum of a catalyst exhibiting high activity is in a reduced state. This is the expression of a so-called metal-support interaction in which the bonding state of carbon atoms on the carbon surface affects the electronic state of platinum. By assuming that the development of sp 2 hybrid carbon atoms no longer shows platinum in this state, the decrease in specific activity in the region of sp 2 / sp 3 > 2.8 can be explained.
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