JP2010275609A - Surface treatment method for particle and particle - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000004381 surface treatment Methods 0.000 title claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 49
- 239000000126 substance Substances 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims description 38
- 239000011248 coating agent Substances 0.000 claims description 37
- 239000003607 modifier Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000002270 dispersing agent Substances 0.000 claims description 11
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical group OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- UGZAJZLUKVKCBM-UHFFFAOYSA-N 6-sulfanylhexan-1-ol Chemical group OCCCCCCS UGZAJZLUKVKCBM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 abstract description 11
- 238000004140 cleaning Methods 0.000 abstract description 5
- 239000002105 nanoparticle Substances 0.000 description 33
- OBACEDMBGYVZMP-UHFFFAOYSA-N iron platinum Chemical compound [Fe].[Fe].[Pt] OBACEDMBGYVZMP-UHFFFAOYSA-N 0.000 description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 14
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000011780 sodium chloride Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910005335 FePt Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CMHKGULXIWIGBU-UHFFFAOYSA-N [Fe].[Pt] Chemical compound [Fe].[Pt] CMHKGULXIWIGBU-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010419 fine particle Substances 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
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 230000005302 magnetic ordering Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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- 230000001131 transforming effect Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000004552 water soluble powder Substances 0.000 description 1
Abstract
Description
本発明は、粒子の表面処理方法及び粒子に関する。 The present invention relates to a particle surface treatment method and particles.
近年、平均径が数１０ｎｍ以下の微粒子であるナノ粒子の研究が盛んに行われている。ナノ粒子の表面は化学的に活性であり、凝集しやすい。このため、ナノ粒子を液相で合成する際には、合成時に安定化剤、例えば有機物を液相に添加することが多い。このようにすると、安定化剤がナノ粒子の表面を被覆するため、ナノ粒子の凝集が抑制される。 In recent years, research on nanoparticles, which are fine particles having an average diameter of several tens of nm or less, has been actively conducted. The surface of the nanoparticles is chemically active and tends to aggregate. For this reason, when the nanoparticles are synthesized in the liquid phase, a stabilizer, for example, an organic substance is often added to the liquid phase during the synthesis. If it does in this way, since a stabilizer coat | covers the surface of a nanoparticle, aggregation of a nanoparticle is suppressed.
ナノ粒子の表面に対する安定化剤の吸着形態には、大きく分けて二種類ある。第一は、安定化剤が動的にナノ粒子表面で吸脱着を繰り返している状態（動的安定化）であり、第二は、ナノ粒子表面に強固に吸着している状態(静的安定化)である。 There are roughly two types of adsorption forms of the stabilizer on the surface of the nanoparticles. The first is a state in which the stabilizer dynamically absorbs and desorbs on the nanoparticle surface (dynamic stabilization), and the second is a state in which the stabilizer is firmly adsorbed on the nanoparticle surface (static stability). ).
なお、特許文献１には、ナノ粒子を噴霧熱分解法により合成する時に水溶性塩を使用し、合成したナノ粒子を水洗することにより、ナノ粒子から水溶性塩を除去することが記載されている。 Patent Document 1 describes that a water-soluble salt is used when a nanoparticle is synthesized by spray pyrolysis, and the synthesized nanoparticle is washed with water to remove the water-soluble salt from the nanoparticle. Yes.
また非特許文献１，２には、水溶性塩にナノ粒子を担持させ、ナノ粒子及び水溶性塩を加熱処理し、結晶系を変態させ、水で塩を溶解除去することにより、アニールした粒子を得ることが記載されている。 In Non-Patent Documents 1 and 2, annealed particles are prepared by supporting nanoparticles in a water-soluble salt, heat-treating the nanoparticles and the water-soluble salt, transforming the crystal system, and dissolving and removing the salt with water. Is described.
ナノ粒子などの粒子を使用する場合、粒子の表面を被覆する物質を安定化剤から他の物質に置き換える必要があることがある。動的安定化の場合は、安定化剤を他の物質へ徐々に置き換えることができるが、静的安定化の場合は、安定化剤を粒子の表面から一回除去し、その後粒子の表面を他の物質で被覆する必要がある。しかし、安定化剤を除去すると、他の物質を被覆する前に粒子が凝集してしまい、他の物質を粒子の表面に被覆することが難しくなる。 When using particles such as nanoparticles, it may be necessary to replace the material that coats the surface of the particle with other materials from the stabilizer. In the case of dynamic stabilization, the stabilizer can be gradually replaced by other substances, but in the case of static stabilization, the stabilizer is removed once from the surface of the particle, and then the surface of the particle is removed. It is necessary to coat with other substances. However, if the stabilizer is removed, the particles aggregate before being coated with another substance, making it difficult to coat the surface of the particle with the other substance.
本発明は上記事情に鑑みてなされたものであり、その目的とするところは、安定化剤などの被覆膜が粒子の表面を静的安定化の状態で被覆している場合であっても、粒子の表面に位置する被覆膜を他の物質に置き換えることができる粒子の表面処理方法及び粒子を提供することにある。 The present invention has been made in view of the above circumstances, and the object of the present invention is even when a coating film such as a stabilizer coats the surface of particles in a state of static stabilization. Another object of the present invention is to provide a particle surface treatment method and particle capable of replacing the coating film located on the surface of the particle with another substance.
本発明によれば、第１の液体に溶解する被覆膜に被覆され、かつ第２の液体及び前記第１の液体に溶解しない粒子を、前記第２の液体に溶解する担持体に担持させる担持工程と、
前記粒子を担持した前記担持体を、前記第１の液体で洗浄することにより、前記粒子の表面から前記被覆膜を部分的に除去する洗浄工程と、
前記担持体を前記第２の液体で溶解する溶解工程と、
を有する粒子の表面処理方法が提供される。
According to the present invention, the second liquid and the particles not dissolved in the first liquid, which are covered with the coating film dissolved in the first liquid, are carried on the carrier that dissolves in the second liquid. A loading process;
A washing step of partially removing the coating film from the surface of the particles by washing the carrier carrying the particles with the first liquid;
A dissolving step of dissolving the carrier with the second liquid;
There is provided a method for surface treatment of particles comprising
本発明によれば、表面を分散剤で被覆された粒子の前記表面から、前記分散剤を部分的に除去する工程と、
前記分散剤が部分的に除去された前記粒子を含む液体中に表面修飾剤を添加して、前記粒子の表面に前記表面修飾剤を被覆する被覆工程と、
を有する粒子の表面処理方法が提供される。
According to the present invention, the step of partially removing the dispersant from the surface of the particles whose surfaces are coated with the dispersant;
A coating step of coating the surface modifier on the surface of the particles by adding a surface modifier to the liquid containing the particles from which the dispersant has been partially removed;
There is provided a method for surface treatment of particles comprising
本発明によれば、表面の一部が分散剤により被覆されており、かつ前記表面の残りの部分が表面修飾剤により被覆された粒子が提供される。
また本発明によれば、上記した方法により表面の一部が表面修飾剤で被覆された粒子が提供される。
According to the present invention, there is provided a particle in which a part of the surface is coated with a dispersant and the remaining part of the surface is coated with a surface modifier.
Moreover, according to this invention, the particle | grains by which one part of the surface was coat | covered with the surface modifier by the above-mentioned method are provided.
本発明によれば、粒子の表面に位置する被覆膜を他の物質に置き換えることができる。 According to the present invention, the coating film located on the surface of the particle can be replaced with another substance.
以下、本発明の実施の形態について、図面を用いて説明する。尚、すべての図面において、同様な構成要素には同様の符号を付し、適宜説明を省略する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.
（第１の実施形態）
図１は、第１の実施形態に係る粒子の表面処理方法を示すフローチャートである。図２の各図は、図１のステップＳ１０〜Ｓ３０及びステップＳ５０の各工程における粒子１０の状態を模式的に示す図である。
(First embodiment)
FIG. 1 is a flowchart showing a particle surface treatment method according to the first embodiment. 2 is a diagram schematically showing the state of the particle 10 in each step of Steps S10 to S30 and Step S50 of FIG.
この粒子１０の表面処理方法は、担持工程（図１のステップＳ１０及び図２（ａ））、洗浄工程（図１のステップＳ２０及び図２（ｂ））、並びに溶解工程（図１のステップＳ３０及び図２（ｃ））を備える。 The surface treatment method of the particles 10 includes a supporting process (step S10 in FIG. 1 and FIG. 2A), a cleaning process (step S20 in FIG. 1 and FIG. 2B), and a dissolving process (step S30 in FIG. 1). And FIG. 2 (c)).
担持工程（ステップＳ１０）では、粒子１０を担持体２０に担持させる。粒子１０は被覆膜１２に静的安定化の状態で被覆されている。被覆膜１２は、第１の液体に溶解する。また粒子１０は、第１の液体に溶解しない。被覆膜１２に被覆された粒子１０は、第１の液体（例えば水やエタノールなどの極性溶媒）に分散しないが、担持体２０は第１の液体に分散する。 In the carrying step (step S10), the particles 10 are carried on the carrier 20. The particles 10 are coated on the coating film 12 in a state of static stabilization. The coating film 12 is dissolved in the first liquid. Further, the particles 10 are not dissolved in the first liquid. The particles 10 covered with the coating film 12 are not dispersed in the first liquid (for example, a polar solvent such as water or ethanol), but the carrier 20 is dispersed in the first liquid.
洗浄工程（ステップＳ２０）では、粒子１０を担持した担持体２０を第１の液体で洗浄する。この工程において、担持体２０は第１の液体に分散するため、粒子１０も担持体２０とともに分散する。そして粒子１０を被覆する被覆膜１２は部分的に除去されるが、粒子１０及び担持体２０は全部又はほとんど残る。この工程において、担持体２０は一部が溶解しても問題ない。 In the washing step (step S20), the carrier 20 carrying the particles 10 is washed with the first liquid. In this step, since the carrier 20 is dispersed in the first liquid, the particles 10 are also dispersed together with the carrier 20. The coating film 12 covering the particles 10 is partially removed, but all or almost all of the particles 10 and the carrier 20 remain. In this step, there is no problem even if the carrier 20 is partially dissolved.
溶解工程（ステップＳ３０）では、担持体２０を第２の液体で溶解する。これにより、被覆膜１２で部分的に被覆された粒子１０を回収することができる。 In the dissolving step (step S30), the carrier 20 is dissolved with the second liquid. Thereby, the particles 10 partially covered with the coating film 12 can be recovered.
粒子１０は、例えばいわゆるナノ粒子であり、粒子の球相当径の平均値が１ｎｍ以上１００ｎｍ以下である。ただし粒子１０の球相当径の平均値はこの範囲に限られず、第一の液体で処理を行う間、担持体２０に担持され続けることができる大きさであればよい。例えば５００μｍ以下であればよい。粒子１０は、例えば白金粒子や白金‐鉄粒子など、白金を含んでいる粒子であるが、他の粒子、例えば金、銀、銅、パラジウム、及びルテニウムからなる群から選ばれた一つ又は複数からなる粒子であってもよい。 The particles 10 are, for example, so-called nanoparticles, and the average value of the equivalent sphere diameters of the particles is 1 nm to 100 nm. However, the average value of the equivalent sphere diameters of the particles 10 is not limited to this range, and may be a size that can continue to be supported on the support 20 during the treatment with the first liquid. For example, it may be 500 μm or less. The particles 10 are particles containing platinum, such as platinum particles and platinum-iron particles, but other particles, for example, one or more selected from the group consisting of gold, silver, copper, palladium, and ruthenium. The particle | grains which consist of may be sufficient.
被覆膜１２は、粒子１０が水などの液体中で凝集することを抑制する分散剤であり、例えばオレイン酸やオレイルアミンなどの有機物、またはこれらが粒子１０を合成するときの加熱工程で変成した有機物である。この場合、第１の液体は、例えば６０％過塩素酸溶液などの酸水溶液であり、有機物の除去に使用される液体である。ただし第１の液体は、これらの例に限定されるものではなく、例えば被覆膜１２が有機物以外の膜である場合には、被覆膜１２の種類によって適宜選択することができる。 The coating film 12 is a dispersant that suppresses the aggregation of the particles 10 in a liquid such as water. For example, an organic material such as oleic acid or oleylamine, or these are modified in the heating process when the particles 10 are synthesized. Organic matter. In this case, the first liquid is an aqueous acid solution such as a 60% perchloric acid solution, and is a liquid used for removing organic substances. However, the first liquid is not limited to these examples. For example, when the coating film 12 is a film other than an organic substance, the first liquid can be appropriately selected depending on the type of the coating film 12.
第２の液体は、例えば水である。ここで用いる水は、純水であってもよいが、溶質が溶解していても良いし、第１の液体と溶質の濃度が異なる液体であっても良い。この場合、担持体２０は、水溶性の粉末、例えば塩化ナトリウムなどの水溶性塩粉末である。ただし担持体２０は、これらの例に限定されるものではなく、例えば第２の液体が水以外である場合には、第２の液体の種類によって、この液体に溶解する物質を担持体２０として適宜選択することができる。 The second liquid is, for example, water. The water used here may be pure water, but a solute may be dissolved, or a liquid having a different solute concentration from the first liquid. In this case, the carrier 20 is a water-soluble powder, for example, a water-soluble salt powder such as sodium chloride. However, the carrier 20 is not limited to these examples. For example, when the second liquid is other than water, a substance that dissolves in the liquid is used as the carrier 20 depending on the type of the second liquid. It can be selected appropriately.
上記したように、ステップＳ１０において、粒子１０は担持体２０に担持されている。このため、第１の液体での洗浄時間を調節することにより、容易に被覆膜１２を粒子１０の表面から部分的に除去した状態にすることができる。 As described above, the particles 10 are carried on the carrier 20 in step S10. For this reason, it is possible to easily remove the coating film 12 from the surface of the particle 10 by adjusting the cleaning time with the first liquid.
そして本実施形態では、さらに溶解工程（図１のステップＳ３０及び図２（ｃ））の後に、分離工程（図１のステップＳ４０）並びに被覆工程（図１のステップＳ５０及び図２（ｄ））を有する。分離工程（ステップＳ４０）では、第２の液体から粒子１０を分離する。この工程は、例えば粒子１０を第２の液体中で遠沈させ、沈殿物を分離することにより行われるが、限外ろ過などの他の方法により行われても良い。なお沈殿物は、分離された後に純水などの溶媒などで洗浄されるのが好ましい。 In this embodiment, after the dissolution process (step S30 in FIG. 1 and FIG. 2C), the separation process (step S40 in FIG. 1) and the coating process (step S50 in FIG. 1 and FIG. 2D). Have In the separation step (step S40), the particles 10 are separated from the second liquid. This step is performed, for example, by centrifuging the particles 10 in the second liquid and separating the precipitate, but may be performed by other methods such as ultrafiltration. The precipitate is preferably washed with a solvent such as pure water after being separated.
被覆工程（ステップＳ５０）では、分離物に表面修飾剤を添加して、粒子１０の表面に表面修飾剤１４を被覆する。この工程は、例えば分離物を分散させた純水に表面修飾剤を添加することにより、行われる。表面修飾剤は、例えばメルカプト酢酸や６−メルカプト−１−ヘキサノールなど、極性基をもつメルカプタンであるが、カルボン酸やアミンなどの金属に配位しやすい他の物質であっても良い。 In the coating step (step S50), a surface modifier is added to the separated substance, and the surface modifier 14 is coated on the surfaces of the particles 10. This step is performed, for example, by adding a surface modifier to pure water in which a separated product is dispersed. The surface modifier is a mercaptan having a polar group, such as mercaptoacetic acid or 6-mercapto-1-hexanol, but may be another substance that easily coordinates to a metal such as carboxylic acid or amine.
上記したように、ステップＳ２０において、被覆膜１２は粒子１０の表面から部分的に除去されている。このため、ステップＳ５０において表面修飾剤１４は、少なくとも粒子１０の表面のうち被覆膜１２により被覆されていない部分に付着する。なお表面修飾剤１４と被覆膜１２の組み合わせによっては、被覆膜１２の表面も表面修飾剤１４により被覆されることもある。 As described above, in step S <b> 20, the coating film 12 is partially removed from the surface of the particle 10. For this reason, in step S50, the surface modifier 14 adheres to at least a portion of the surface of the particle 10 that is not covered with the coating film 12. Depending on the combination of the surface modifier 14 and the coating film 12, the surface of the coating film 12 may be coated with the surface modifier 14.
その後、粒子１０は、遠沈及び洗浄が行われることにより、水から分離される。この状態において、粒子１０は、表面の一部が被覆膜１２により被覆されており、かつ表面の残りの部分が表面修飾剤１４により被覆されている。粒子１０の表面のうち被覆膜１２に被覆されている部分は、粒子１０が鉄白金ナノ粒子で被覆膜１２が有機物であり、組成分析（微量分析）の結果に基づいて算出した場合、表面全体の１０％以上３０％以下である。 Thereafter, the particles 10 are separated from the water by centrifugation and washing. In this state, a part of the surface of the particle 10 is covered with the coating film 12, and the remaining part of the surface is covered with the surface modifier 14. The portion of the surface of the particle 10 covered with the coating film 12 is calculated based on the result of the composition analysis (trace analysis) when the particle 10 is iron platinum nanoparticles and the coating film 12 is an organic substance. It is 10% or more and 30% or less of the entire surface.
次に、本実施形態の作用及び効果について説明する。上記したように、粒子１０の表面を静的安定化の状態で被覆している被覆膜１２は、洗浄工程（ステップＳ２０）において部分的に除去されている。言い換えれば、洗浄工程の後においても粒子１０の表面は、被覆膜１２によって部分的に被覆されている。このため、溶解工程（ステップＳ３０）により担持体２０を第２の液体に溶解した後においても、粒子１０が凝集することを抑制できる。この効果は、粒子１０の粒子径が小さい場合に特に顕著になる。このため、溶解工程の後において、粒子１０の表面に表面修飾剤１４を容易に付着させることができる。 Next, the operation and effect of this embodiment will be described. As described above, the coating film 12 covering the surfaces of the particles 10 in a statically stabilized state is partially removed in the cleaning step (step S20). In other words, the surface of the particle 10 is partially covered with the coating film 12 even after the cleaning step. For this reason, even after the carrier 20 is dissolved in the second liquid by the dissolving step (step S30), the aggregation of the particles 10 can be suppressed. This effect is particularly remarkable when the particle diameter of the particles 10 is small. For this reason, the surface modifier 14 can be easily attached to the surface of the particle 10 after the dissolution step.
（第２の実施形態）
図３は、第２の実施形態に係る粒子の表面処理方法を示すフローチャートである。本実施形態に係る粒子の表面処理方法は、分離工程（図１のステップＳ４０）がない点を除いて、第１の実施形態に係る粒子の表面処理方法と同様である。すなわち本実施形態では、被覆工程（ステップＳ５０）は、担持体２０が溶解していて粒子１０が分散している第２の液体に表面修飾剤を添加することにより、行われる。
(Second Embodiment)
FIG. 3 is a flowchart showing the particle surface treatment method according to the second embodiment. The particle surface treatment method according to the present embodiment is the same as the particle surface treatment method according to the first embodiment, except that there is no separation step (step S40 in FIG. 1). That is, in this embodiment, the coating step (step S50) is performed by adding a surface modifier to the second liquid in which the support 20 is dissolved and the particles 10 are dispersed.
本実施形態によっても、第１の実施形態と同様の効果を得ることができる。 Also according to this embodiment, the same effect as that of the first embodiment can be obtained.
以上、図面を参照して本発明の実施形態について述べたが、これらは本発明の例示であり、上記以外の様々な構成を採用することもできる。 As mentioned above, although embodiment of this invention was described with reference to drawings, these are the illustrations of this invention, Various structures other than the above are also employable.
（実施例）
粒子１０として鉄白金ナノ粒子を使用し、担持体２０として塩化ナトリウムを使用し、第１の液体として６０重量％の過塩素酸水溶液を使用し、第２の液体として純水を使用した。粒子１０の表面を被覆している分散剤は有機物であり、水やエタノールなどの極性溶媒には分散しない。以下、実施例における処理フローについて、図４を用いて詳細に説明する。
(Example)
Iron platinum nanoparticles were used as the particles 10, sodium chloride was used as the carrier 20, a 60 wt% aqueous perchloric acid solution was used as the first liquid, and pure water was used as the second liquid. The dispersant covering the surface of the particle 10 is an organic substance and is not dispersed in a polar solvent such as water or ethanol. Hereinafter, the processing flow in the embodiment will be described in detail with reference to FIG.
まず、１ｇの塩化ナトリウム（担持体２０）を乳鉢で粉砕した後、１０ｍｇの鉄白金ナノ粒子（粒子１０）の乾燥粉体を乳鉢に加え、全体がねずみ色になるまで十分混合した（ステップＳ１１０）。次いで、この混合粉末を、ガラス製の５０ｍＬのバイアル瓶にいれ、さらに６０重量％の過塩素酸水溶液を５ｍＬこのバイアル瓶にいれた。そしてバイアル瓶を、予め５５℃に加熱した超音波照射装置で５分間処理し、過塩素酸水溶液中に塩化ナトリウムと鉄白金ナノ粒子の混合粉末を分散させた（ステップＳ１２０）。 First, 1 g of sodium chloride (support 20) was pulverized in a mortar, and then 10 mg of dry powder of iron platinum nanoparticles (particles 10) was added to the mortar and mixed well until the whole became a gray color (step S110). . Then, this mixed powder was put into a glass-made 50 mL vial, and further 60 mL of a perchloric acid aqueous solution was put into the vial. Then, the vial was treated for 5 minutes with an ultrasonic irradiation device heated to 55 ° C. in advance to disperse the mixed powder of sodium chloride and iron platinum nanoparticles in the perchloric acid aqueous solution (step S120).
次いで、バイアル瓶の中の過塩素酸水溶液を３５ｍＬの純水で希釈した（ステップＳ１３０）。このとき担持体２０としての塩化ナトリウムは溶解した。その後、バイアル瓶の中の過塩素酸水溶液に含まれる粉末を遠沈させ、上澄みを除去して沈殿物を分離した（ステップＳ１４０）。その後、沈殿物を純水に分散させ（ステップＳ１５０）、この分散液のｐＨを測定した。ｐＨが５以上６以下になるまで、ステップＳ１４０及びステップＳ１５０の処理を繰り返した（ステップＳ１６０）。 Next, the perchloric acid aqueous solution in the vial was diluted with 35 mL of pure water (step S130). At this time, sodium chloride as the carrier 20 was dissolved. Thereafter, the powder contained in the perchloric acid aqueous solution in the vial was spun down, the supernatant was removed, and the precipitate was separated (step S140). Thereafter, the precipitate was dispersed in pure water (step S150), and the pH of this dispersion was measured. The processes of step S140 and step S150 were repeated until the pH became 5 or more and 6 or less (step S160).
その後、分散液を再び遠沈させ、上澄みを除去することにより沈殿物を分離し（ステップＳ１７０）、沈殿物に表面修飾剤が溶解した溶液を添加して超音波処理装置で処理した（ステップＳ１８０）。その後、遠沈を行い、表面修飾剤により被覆された鉄白金ナノ粒子を回収した。なお、表面修飾剤が溶解した溶液としてメルカプト酢酸が溶解した水を使用した場合、回収した鉄白金ナノ粒子は水のみに分散し、６−メルカプト−１−ヘキサノールが溶解したエタノールを使用した場合、回収した鉄白金ナノ粒子はエタノールに分散し、水には分散しなかった。 Thereafter, the dispersion is spun down again, and the precipitate is separated by removing the supernatant (step S170), and a solution in which the surface modifier is dissolved is added to the precipitate and processed by an ultrasonic treatment device (step S180). ). Thereafter, centrifugation was performed to collect iron platinum nanoparticles coated with the surface modifier. In addition, when water in which mercaptoacetic acid is dissolved is used as the solution in which the surface modifier is dissolved, the recovered iron platinum nanoparticles are dispersed only in water, and when ethanol in which 6-mercapto-1-hexanol is dissolved is used, The recovered iron platinum nanoparticles were dispersed in ethanol and not dispersed in water.
図５（ａ）は、ステップＳ１８０において表面修飾剤が溶解した溶液としてメルカプト酢酸が溶解した水を使用した場合の鉄白金ナノ粒子のＴＥＭ写真であり、図５（ｂ）は、ステップＳ１８０において表面修飾剤が溶解した溶液として６−メルカプト−１−ヘキサノールが溶解したエタノールを使用した場合の鉄白金ナノ粒子のＴＥＭ写真である。これらの写真から、鉄白金ナノ粒子は水またはエタノールに分散することが示された。 FIG. 5 (a) is a TEM photograph of iron platinum nanoparticles when water in which mercaptoacetic acid is dissolved is used as the solution in which the surface modifier is dissolved in step S180, and FIG. 5 (b) is the surface in step S180. It is a TEM photograph of iron platinum nanoparticles when ethanol in which 6-mercapto-1-hexanol is dissolved is used as the solution in which the modifier is dissolved. From these photographs, it was shown that iron platinum nanoparticles were dispersed in water or ethanol.
表１は、図４のステップＳ１１０〜Ｓ１７０に示した処理を行う前及び後それぞれの鉄白金ナノ粒子に含まれる炭素、水素、及び窒素の量を、微量分析装置（エレメンタール社製 ｖａｒｉｏＥＬ）で分析した結果を示している。 Table 1 shows the amounts of carbon, hydrogen, and nitrogen contained in each iron platinum nanoparticle before and after performing the processing shown in steps S110 to S170 of FIG. 4 using a microanalyzer (varioEL manufactured by Elemental Co., Ltd.). The analysis results are shown.
この表に示すように、過塩素酸水溶液によって鉄白金ナノ粒子を担持した塩化ナトリウムを処理すること（ステップＳ１２０）により、炭素及び水素が、それぞれ０．４％減少したが、炭素及び水素は、何れも残存している。これらのことから、ステップＳ１２０に示した処理により、鉄白金ナノ粒子の表面を被覆している分散剤が、部分的に除去されたと推定できる。 As shown in this table, by treating sodium chloride carrying iron platinum nanoparticles with a perchloric acid aqueous solution (step S120), carbon and hydrogen were reduced by 0.4%, respectively. Both remain. From these facts, it can be presumed that the dispersant covering the surface of the iron-platinum nanoparticles has been partially removed by the process shown in step S120.
また、ステップＳ１３０，１５０の各工程において、鉄白金ナノ粒子が凝集することはなかった。このため、ステップＳ１８０において、鉄白金ナノ粒子の表面に表面修飾剤が効率よく付着したと考えられる。 Moreover, in each process of step S130,150, the iron platinum nanoparticle did not aggregate. For this reason, in step S180, it is thought that the surface modifier adhered to the surface of the iron platinum nanoparticles efficiently.
１０ 粒子
１２ 被覆膜
１４ 表面修飾剤
２０ 担持体
10 Particles 12 Coating film 14 Surface modifier 20 Carrier
Claims (9)
前記粒子を担持した前記担持体を、前記第１の液体で洗浄することにより、前記粒子の表面から前記被覆膜を部分的に除去する洗浄工程と、
前記担持体を前記第２の液体で溶解する溶解工程と、
を有する粒子の表面処理方法。 A supporting step of supporting particles that are coated with a coating film that dissolves in the first liquid and that do not dissolve in the second liquid and the first liquid, on a carrier that dissolves in the second liquid;
A washing step of partially removing the coating film from the surface of the particles by washing the carrier carrying the particles with the first liquid;
A dissolving step of dissolving the carrier with the second liquid;
A surface treatment method of particles having
前記溶解工程の後に、
前記担持体が溶解して前記粒子を含む前記第２の液体に表面修飾剤を添加して、前記粒子の表面に前記表面修飾剤を被覆する被覆工程を有する粒子の表面処理方法。 The particle surface treatment method according to claim 1,
After the dissolving step,
A particle surface treatment method comprising a coating step of coating the surface modifier with a surface modifier added to the second liquid containing the particles after the carrier is dissolved.
前記溶解工程の後に、
前記第２の液体から、前記粒子を含む分離物を分離する分離工程と、
前記分離物に表面修飾剤を添加して、前記粒子の表面に前記表面修飾剤を被覆する被覆工程と、
を有する粒子の表面処理方法。 The particle surface treatment method according to claim 1,
After the dissolving step,
A separation step of separating a separation containing the particles from the second liquid;
A coating step of adding a surface modifier to the separated material and coating the surface of the particles with the surface modifier;
A surface treatment method of particles having
前記被覆膜は有機物であり、前記第１の液体は酸水溶液であり、前記第２の液体は水である粒子の表面処理方法。 In the surface treatment method of the particle as described in any one of Claims 1-3,
The surface treatment method for particles, wherein the coating film is an organic substance, the first liquid is an acid aqueous solution, and the second liquid is water.
前記分散剤が部分的に除去された前記粒子を含む液体中に表面修飾剤を添加して、前記粒子の表面に前記表面修飾剤を被覆する被覆工程と、
を有する粒子の表面処理方法。 Partially removing the dispersant from the surface of the particles whose surfaces are coated with the dispersant;
A coating step of coating the surface modifier on the surface of the particles by adding a surface modifier to the liquid containing the particles from which the dispersant has been partially removed;
A surface treatment method of particles having
前記表面修飾剤は、メルカプト酢酸である粒子。 The particle according to claim 6 or 7,
Particles wherein the surface modifier is mercaptoacetic acid.
前記表面修飾剤は、６−メルカプト−１−ヘキサノールである粒子。 The particle according to claim 7 or 8,
Particles wherein the surface modifier is 6-mercapto-1-hexanol.
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