JP2010285669A - Method for producing metal particle, metal particle, and metal particle production device - Google Patents
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- 239000002923 metal particle Substances 0.000 title claims abstract description 79
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 150000002736 metal compounds Chemical group 0.000 claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 claims abstract description 58
- 239000002184 metal Substances 0.000 claims abstract description 58
- 238000010438 heat treatment Methods 0.000 claims abstract description 35
- 239000006227 byproduct Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 230000008859 change Effects 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 239000011247 coating layer Substances 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- 238000006722 reduction reaction Methods 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 4
- -1 heat-treating Substances 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 125000002524 organometallic group Chemical group 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 18
- 229910052697 platinum Inorganic materials 0.000 description 18
- 239000002270 dispersing agent Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000004868 gas analysis Methods 0.000 description 7
- 239000005416 organic matter Substances 0.000 description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 7
- 229910001887 tin oxide Inorganic materials 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 2
- BTOOAFQCTJZDRC-UHFFFAOYSA-N 1,2-hexadecanediol Chemical compound CCCCCCCCCCCCCCC(O)CO BTOOAFQCTJZDRC-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229910005335 FePt Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZFSQRSOTOXERMJ-UHFFFAOYSA-N ethanol;iron Chemical compound [Fe].CCO.CCO.CCO ZFSQRSOTOXERMJ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- OBACEDMBGYVZMP-UHFFFAOYSA-N iron platinum Chemical compound [Fe].[Fe].[Pt] OBACEDMBGYVZMP-UHFFFAOYSA-N 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
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Abstract
Description
本発明は、金属粒子の製造方法、金属粒子、及び金属粒子製造装置に関する。 The present invention relates to a method for producing metal particles, metal particles, and a metal particle production apparatus.
不均一触媒に用いられる白金は、埋蔵量が少ない。このため、白金を効率よく利用するために白金を粒子状にして比表面積を大きくすることが望まれている。粒子の比表面積を小さくするためには、粒子の直径を小さくし、かつ粒子の直径の分散を小さくする必要がある。 Platinum used for heterogeneous catalysts has a small reserve. For this reason, in order to use platinum efficiently, it is desired to increase the specific surface area by making platinum particles. In order to reduce the specific surface area of the particles, it is necessary to reduce the particle diameter and to reduce the dispersion of the particle diameter.
白金の粒子を製造する方法の一つに、白金セチルアセトレートを、ポリオールを用いて液相中で還元して分解する方法がある（非特許文献１）。この方法によれば、液相中で白金粒子を製造することができる。白金粒子の直径を小さくし、かつ白金粒子の直径の分散を小さくするためには、白金セチルアセトレートの分解を高温で急激に行うことが望ましい。 One method for producing platinum particles is a method of reducing and decomposing platinum cetylacetolate in a liquid phase using a polyol (Non-patent Document 1). According to this method, platinum particles can be produced in the liquid phase. In order to reduce the diameter of the platinum particles and to reduce the dispersion of the diameter of the platinum particles, it is desirable to rapidly decompose the platinum cetyl acetolate at a high temperature.
一方で、粒子は一般的に小さくなると凝集しやすくなる。このため、上記した方法で白金の粒子を生成するときには、例えば特許文献１に記載するように、生成した白金の表面を分散剤で修飾する必要がある。 On the other hand, particles generally tend to aggregate as they become smaller. For this reason, when producing | generating the particle | grains of platinum with an above-described method, as described in patent document 1, it is necessary to modify the surface of the produced | generated platinum with a dispersing agent.
しかし、分散剤は有機物であることが多く、熱分解を起こしやすい。このため、白金などの金属粒子を高温で生成するときには、分散剤として用いることができる物質は少ない。一方で、金属の種類によっては、高温でも熱分解しにくい有機物を分散剤として用いることができ得る。このため、金属の粒子の表面を他の金属で被覆すると、分散剤として使用できる物質の選択肢が増えると考えられる。 However, the dispersant is often an organic substance and is likely to undergo thermal decomposition. For this reason, when producing metal particles such as platinum at a high temperature, there are few substances that can be used as a dispersant. On the other hand, depending on the type of metal, an organic substance that is difficult to thermally decompose even at high temperatures can be used as a dispersant. For this reason, if the surface of the metal particle is coated with another metal, it is considered that the choice of substances that can be used as a dispersant increases.
金属の粒子を他の金属で被覆する方法としては、第１の金属化合物と第２の金属化合物を同一の容器内で分解する方法が考えられる。この方法により金属の粒子を製造する場合、精度よく金属化合物の分解の度合いを検出する必要がある。 As a method of coating the metal particles with another metal, a method of decomposing the first metal compound and the second metal compound in the same container can be considered. When producing metal particles by this method, it is necessary to accurately detect the degree of decomposition of the metal compound.
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、第１の金属化合物と第２の金属化合物を同一の容器内で分解して金属粒子を製造する場合において、精度よく金属化合物の分解の度合いを検出することができる金属粒子の製造方法、金属粒子、及び金属粒子製造装置を提供することにある。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide accuracy in the case of producing metal particles by decomposing the first metal compound and the second metal compound in the same container. An object of the present invention is to provide a method for producing metal particles, a metal particle, and a metal particle production apparatus capable of well detecting the degree of decomposition of a metal compound.
本発明によれば、第１の金属を含む第１の金属化合物と、第２の金属を含む第２の金属化合物とを含んだ溶媒に、還元剤を導入して熱処理し、
前記溶媒の中で生じる前記第１の金属化合物及び前記第２の金属化合物の還元反応で生成する副生成物の量の経時変化を測定することにより、前記熱処理の終了タイミングを判断する、金属粒子の製造方法が提供される。
According to the present invention, a reducing agent is introduced into a solvent containing a first metal compound containing a first metal and a second metal compound containing a second metal, and heat-treated,
Metal particles for determining the end timing of the heat treatment by measuring the change over time in the amount of by-products generated in the reduction reaction of the first metal compound and the second metal compound generated in the solvent A manufacturing method is provided.
本発明によれば、上記した方法により製造され、第１の金属を含む金属核と、
前記金属核の表面に形成され、第２の金属を含んでいて前記第１の金属を含んでいない被覆層と、
を有している金属粒子が提供される。
According to the present invention, a metal nucleus produced by the above method and containing a first metal;
A coating layer formed on a surface of the metal core and including a second metal and not including the first metal;
There are provided metal particles having
本発明によれば、第１の金属を含む第１の金属化合物、第２の金属を含む第２の金属化合物、溶媒、及び還元剤が導入される反応容器と、
前記反応容器を加熱する加熱部と、
前記反応容器内の雰囲気を分析し、前記第１の金属化合物及び前記第２の金属化合物の還元反応で生成する副生成物の量の経時変化を測定する分析部と、
前記分析部が前記副生成物の量の最大値を検出してから、予め定められた時間が経過した後に前記加熱部による加熱を止める制御部と、
を備える金属粒子製造装置が提供される。
According to the present invention, a reaction vessel into which a first metal compound containing a first metal, a second metal compound containing a second metal, a solvent, and a reducing agent are introduced;
A heating unit for heating the reaction vessel;
An analysis unit that analyzes the atmosphere in the reaction vessel and measures a change over time in the amount of by-products generated in the reduction reaction of the first metal compound and the second metal compound;
A control unit that stops heating by the heating unit after a predetermined time has elapsed since the analysis unit detected the maximum amount of the by-product;
An apparatus for producing metal particles is provided.
本発明によれば、第１の金属化合物と第２の金属化合物を同一の容器内で分解して金属粒子を製造する場合において、精度よく金属化合物の分解の度合いを検出することができる。 According to the present invention, when the metal particles are produced by decomposing the first metal compound and the second metal compound in the same container, the degree of decomposition of the metal compound can be detected with high accuracy.
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.
図１は、実施形態に係る金属粒子製造装置の構成を示すブロック図である。この金属粒子の製造方法は、反応容器１００、加熱部１２０、ガス分析部１４０、及び制御部１６０を備える。反応容器１００は、第１の金属を含む第１の金属化合物、第２の金属を含んでいる第２の金属化合物、溶媒、及び還元剤が導入される。加熱部１２０は、反応容器１００を加熱する。ガス分析部１４０は、反応容器１００内の雰囲気を分析し、第１の金属化合物及び第２の金属化合物の還元反応で生成する副生成物の量の経時変化を測定する。制御部１６０は、加熱部１２０を制御する。詳細には、制御部１６０は、ガス分析部１４０が副生成物の量の最大値を検出してから、予め定められた時間が経過した後に加熱部１２０による加熱を止める。 FIG. 1 is a block diagram illustrating a configuration of a metal particle manufacturing apparatus according to an embodiment. This method for producing metal particles includes a reaction vessel 100, a heating unit 120, a gas analysis unit 140, and a control unit 160. In the reaction vessel 100, a first metal compound containing a first metal, a second metal compound containing a second metal, a solvent, and a reducing agent are introduced. The heating unit 120 heats the reaction vessel 100. The gas analyzer 140 analyzes the atmosphere in the reaction vessel 100 and measures a change over time in the amount of by-products generated by the reduction reaction of the first metal compound and the second metal compound. The control unit 160 controls the heating unit 120. Specifically, the control unit 160 stops heating by the heating unit 120 after a predetermined time has elapsed since the gas analysis unit 140 detected the maximum value of the amount of by-products.
加熱部１２０が反応容器１００を加熱することにより、反応容器１００の中で第１の金属化合物及び第２の金属化合物が還元されて分解し、金属粒子が生成する。本実施形態において、第２の金属化合物は第１の金属化合物より還元しにくい。具体的には、第２の金属のゼロ価状態での相互作用エネルギーは、第１の金属のゼロ価状態での相互作用エネルギーより大きい（負の方向で見た場合には小さい）。このため、第１の金属化合物が先に還元され、第１の金属を主成分とする金属粒子が生成する。金属粒子の球相当径の平均値は、例えば１ｎｍ以上１００ｎｍ以下である。その後、第２の金属化合物が還元され、第１の金属を主成分とする金属粒子を被覆する被覆層が形成される。この被覆層は、第２の金属を含んでおり、第１の金属をほとんど含んでいない。なお、第１の金属は例えば白金であり、第２の金属は例えば鉄である。 When the heating unit 120 heats the reaction vessel 100, the first metal compound and the second metal compound are reduced and decomposed in the reaction vessel 100 to generate metal particles. In the present embodiment, the second metal compound is less likely to be reduced than the first metal compound. Specifically, the interaction energy of the second metal in the zero valence state is greater than the interaction energy of the first metal in the zero valence state (small when viewed in the negative direction). For this reason, a 1st metal compound is reduce | restored previously and the metal particle which has a 1st metal as a main component produces | generates. The average value of the equivalent sphere diameters of the metal particles is, for example, 1 nm or more and 100 nm or less. Thereafter, the second metal compound is reduced to form a coating layer that covers the metal particles containing the first metal as a main component. This coating layer contains the second metal and hardly contains the first metal. Note that the first metal is, for example, platinum, and the second metal is, for example, iron.
第１の金属化合物及び第２の金属化合物は、例えば有機金属である。この場合、金属粒子の生成時に副生成物として有機物が発生する。この有機物は、反応容器１００の中において、溶媒から気化して雰囲気中に含まれる。 The first metal compound and the second metal compound are, for example, organic metals. In this case, an organic substance is generated as a by-product when the metal particles are generated. This organic substance is vaporized from the solvent and contained in the atmosphere in the reaction vessel 100.
反応容器１００の中はガス導入管１０２によってアルゴンなどの不活性ガスが導入され、かつ排気管１０４によって排気されている。排気管１０４によって排出された気体は、ガス分析部１４０に導入される。ガス分析部１４０は、排気管１０４から排気された気体に含まれる副生成物、例えば有機物の量を分析する。 An inert gas such as argon is introduced into the reaction vessel 100 through the gas introduction pipe 102 and exhausted through the exhaust pipe 104. The gas exhausted by the exhaust pipe 104 is introduced into the gas analysis unit 140. The gas analyzer 140 analyzes the amount of by-products, for example, organic substances, contained in the gas exhausted from the exhaust pipe 104.
ガス分析部１４０は、半導体センサー又は赤外吸光（ＩＲ又はＦＴ−ＩＲ）により副生成物を検出する装置である。副生成物が有機物であるとき、半導体センサーは、例えば酸化スズの抵抗変化により副生成物の量を検出する。詳細には、排気管１０４から排気された気体に含まれる有機物は、酸化スズに付着すると、酸化触媒作用により酸化スズ表面の酸素が奪われ、これにより酸化スズの抵抗が減少する。ただし酸化スズに付着する有機物の量が飽和すると、有機物を検出できなくなる。このため、この半導体センサーは、酸化スズを加熱して酸化スズに付着した有機物を酸素で燃焼させて有機物を減らす機能を有している。ガス分析部１４０による測定結果は、制御部１６０に出力される。 The gas analyzer 140 is a device that detects a by-product using a semiconductor sensor or infrared absorption (IR or FT-IR). When the by-product is an organic substance, the semiconductor sensor detects the amount of the by-product by, for example, a change in resistance of tin oxide. Specifically, when the organic matter contained in the gas exhausted from the exhaust pipe 104 adheres to the tin oxide, oxygen on the surface of the tin oxide is deprived by the oxidation catalytic action, thereby reducing the resistance of the tin oxide. However, when the amount of organic matter adhering to tin oxide is saturated, the organic matter cannot be detected. For this reason, this semiconductor sensor has a function of reducing organic matter by heating the tin oxide and burning the organic matter adhering to the tin oxide with oxygen. The measurement result by the gas analyzer 140 is output to the controller 160.
制御部１６０は、上記したように、ガス分析部１４０が副生成物の量の最大値を検出してから、予め定められた時間が経過した後に加熱部１２０による加熱を止める。制御部１６０は、例えば副生成物の量を示すデータを単位時間間隔でガス分析部１４０から取得する。そして制御部１６０は、データを取得するたびに一つ前のデータとの差分を算出する。そして制御部１６０は、その差分が予め定められた回数連続して負の値を示したときに、副生成物の生成量は既にピークを過ぎていると判断する。そして制御部１６０は、副生成物の量が最大値を示していたタイミングを遡って判断し、そのタイミングから予め定められた時間が経過した後に加熱部１２０による加熱を止める。 As described above, the control unit 160 stops heating by the heating unit 120 after a predetermined time has elapsed after the gas analysis unit 140 detects the maximum value of the amount of by-products. For example, the control unit 160 acquires data indicating the amount of by-products from the gas analysis unit 140 at unit time intervals. The control unit 160 calculates a difference from the previous data every time data is acquired. And the control part 160 judges that the production amount of a by-product has already passed the peak, when the difference shows the negative value continuously for the predetermined number of times. And the control part 160 judges retroactively the timing when the quantity of the by-product showed the maximum value, and stops heating by the heating part 120 after the predetermined time has passed from that timing.
図２は、図１に示した金属粒子製造装置を用いて金属粒子を製造する方法を示すフローチャートである。まず反応容器１００に第１の金属化合物、第２の金属化合物、還元剤、及び分散剤を導入する（ステップＳ１０）。第１の金属化合物及び第２の金属化合物は、例えば有機金属であり、例えば白金アセチルアセトレート及び鉄アセチルアセトレートである。還元剤は、１，２−ヘキサデカンジオールなどのポリオールである。分散剤は、例えばオレイン酸やオレイルアミンなどの有機物であるが、この場合、分散剤が溶媒を兼ねる。 FIG. 2 is a flowchart showing a method for producing metal particles using the metal particle production apparatus shown in FIG. First, the first metal compound, the second metal compound, the reducing agent, and the dispersing agent are introduced into the reaction vessel 100 (step S10). The first metal compound and the second metal compound are, for example, organic metals, such as platinum acetylacetolate and iron acetylacetolate. The reducing agent is a polyol such as 1,2-hexadecanediol. The dispersant is, for example, an organic substance such as oleic acid or oleylamine. In this case, the dispersant also serves as a solvent.
次いで制御部１６０は加熱部１２０を制御して反応容器１００を加熱し、所定の温度、例えば３００℃で保持する。このとき、反応容器１００にはガス導入管１０２から不活性ガスが導入され続け、これに伴って排気管１０４からは反応容器１００の中の雰囲気ガスが排気され続ける。そしてガス分析部１４０は、排気管１０４から排気されたガスの中に含まれる副生成物、例えば有機物の濃度を所定時間間隔で測定する（ステップＳ２０）。ガス分析部１４０による測定結果は、制御部１６０に出力される。 Next, the control unit 160 controls the heating unit 120 to heat the reaction vessel 100 and hold it at a predetermined temperature, for example, 300 ° C. At this time, the inert gas is continuously introduced into the reaction vessel 100 from the gas introduction tube 102, and the atmospheric gas in the reaction vessel 100 is continuously exhausted from the exhaust tube 104 along with this. Then, the gas analyzer 140 measures the concentration of by-products, for example, organic substances contained in the gas exhausted from the exhaust pipe 104 at predetermined time intervals (step S20). The measurement result by the gas analyzer 140 is output to the controller 160.
そして制御部１６０は、ガス分析部１４０による測定結果を処理し、副生成物の濃度がピークを迎えたか否かを判断する。副生成物の濃度がピークを迎えたことが検出できたとき（ステップＳ３０：Ｙｅｓ）、副生成物の濃度がピークを迎えたタイミング、すなわちガス分析部１４０による測定結果が最大値を示したタイミングを認識する。そして、認識したタイミングから予め定められた時間（例えば１０分）が経過した後に、加熱部１２０による加熱を終了し、反応容器１００の冷却を開始する（ステップＳ４０）。 And the control part 160 processes the measurement result by the gas analysis part 140, and judges whether the density | concentration of the by-product reached the peak. When it is detected that the concentration of the by-product has reached the peak (step S30: Yes), the timing at which the concentration of the by-product has reached the peak, that is, the timing when the measurement result by the gas analyzer 140 shows the maximum value. Recognize And after predetermined time (for example, 10 minutes) passes from the recognized timing, the heating by the heating part 120 is complete | finished and cooling of the reaction container 100 is started (step S40).
反応容器１００が十分冷却された後、反応容器１００の中の溶液を、例えば、ヘキサンを加えて希釈してから取り出し、エタノールを加え、金属粒子に対して貧溶媒としてから、 遠心分離して、生成物を沈殿させる（遠沈法）。そして沈殿物すなわち金属粒子を上澄みから分離する（ステップＳ５０）。この状態において、金属粒子は、第１の金属を含む金属核と被覆層とを有している。被覆層は金属核の表面に形成され、第２の金属を含んでいて第１の金属を含んでいない。第１の金属化合物と第２の金属化合物がそれぞれ白金アセチルアセトレートと鉄アセチルアセトレートであるとき、金属核は白金であり、被覆層は鉄を含む層、例えば酸化鉄である。 After the reaction vessel 100 is sufficiently cooled, the solution in the reaction vessel 100 is taken out after being diluted with, for example, hexane, added with ethanol, made a poor solvent for the metal particles, and then centrifuged. The product is precipitated (centrifuge method). Then, precipitates, that is, metal particles are separated from the supernatant (step S50). In this state, the metal particles have a metal nucleus containing the first metal and a coating layer. The coating layer is formed on the surface of the metal core and contains the second metal and does not contain the first metal. When the first metal compound and the second metal compound are platinum acetylacetolate and iron acetylacetolate, respectively, the metal nucleus is platinum, and the coating layer is a layer containing iron, for example, iron oxide.
その後、分離した金属粒子を、被覆層を溶かすための薬液の中に分散させる。被覆層が鉄を含む層であるとき、薬液は酸性溶液である。これにより金属粒子から被覆層が除去され、第１の金属を含む金属核が金属粒子として得られる（ステップＳ６０）。 Thereafter, the separated metal particles are dispersed in a chemical solution for dissolving the coating layer. When the coating layer is a layer containing iron, the chemical solution is an acidic solution. As a result, the coating layer is removed from the metal particles, and metal nuclei containing the first metal are obtained as metal particles (step S60).
図３は、図２に示した工程において金属粒子がどのように生成するかを模式的に示す図である。本図に示す例において、第１の金属化合物は第２の金属化合物より還元剤により分解しやすい。 FIG. 3 is a diagram schematically showing how metal particles are generated in the process shown in FIG. In the example shown in the figure, the first metal compound is more easily decomposed by the reducing agent than the second metal compound.
まず図２のステップＳ２０において、第１の金属化合物が第２の金属化合物より先に分解される。これにより、図３（ａ）に示すように金属核１０が形成される。第１の金属化合物のほとんどが分解されると、その後、第２の金属化合物の分解が始まる。これにより、図３（ｂ）に示すように、金属核１０の表面に被覆層２０が成長し始める。例えば金属核１０より被覆層２０のほうが分散剤３０が吸着しやすい場合、図３（ｃ）に示すように、分散剤３０は、被覆層２０が成長し始めてから金属粒子の被覆層２０に付着する。その後、被覆層２０が成長して、図３（ｄ）に示すように金属核１０の略全面が被覆層２０及び分散剤３０によって被覆される。 First, in step S20 of FIG. 2, the first metal compound is decomposed before the second metal compound. Thereby, the metal nucleus 10 is formed as shown in FIG. When most of the first metal compound is decomposed, then the second metal compound starts to decompose. Thereby, as shown in FIG. 3B, the coating layer 20 starts to grow on the surface of the metal core 10. For example, when the coating layer 20 is more easily adsorbed than the metal core 10, the dispersing agent 30 adheres to the coating layer 20 of metal particles after the coating layer 20 starts to grow as shown in FIG. To do. Thereafter, the coating layer 20 grows, and substantially the entire surface of the metal core 10 is coated with the coating layer 20 and the dispersant 30 as shown in FIG.
この段階になる手前のいずれかのタイミングで、反応容器１００から排気される雰囲気ガスに含まれる副生成物の濃度は、ピークを迎えると考えられる。そして、ピークを迎えてから予め定められた時間が経過した後に加熱を終了させると、被覆層２０と金属核１０が合金化することを抑制できる。 It is considered that the concentration of by-products contained in the atmospheric gas exhausted from the reaction vessel 100 reaches a peak at any timing before reaching this stage. And if heating is complete | finished after predetermined time passes after reaching a peak, it can suppress that the coating layer 20 and the metal nucleus 10 alloy.
そして図２のステップＳ６０において金属粒子を薬液で処理する。これにより、図３（ｅ）に示すように、被覆層２０及び分散剤３０が除去されていき、最終的には図３（ｆ）に示すように金属核１０のみとなる。 In step S60 of FIG. 2, the metal particles are treated with a chemical solution. Thereby, as shown in FIG. 3E, the coating layer 20 and the dispersant 30 are removed, and finally, only the metal core 10 is obtained as shown in FIG.
以上、本実施形態によれば、金属化合物の還元反応で生じる副生成物の量の経時変化、例えば反応容器１００から排気される雰囲気ガスに含まれる副生成物の濃度を測定することにより、反応容器１００の熱処理の終了タイミングを判断する。このため、精度よく金属化合物の分解の度合いを検出することができる。 As described above, according to the present embodiment, the reaction by measuring the change over time of the amount of by-products generated in the reduction reaction of the metal compound, for example, the concentration of by-products contained in the atmospheric gas exhausted from the reaction vessel 100. The end timing of the heat treatment of the container 100 is determined. For this reason, the degree of decomposition of the metal compound can be detected with high accuracy.
このため、例えば金属核１０の表面を被覆層２０が被覆する場合において、被覆層２０と金属核１０が合金化する前に加熱を終了することができる。従って、金属核１０に対して分散剤３０として働く材料がない場合でも、被覆層２０に分散剤として働く材料を用いることにより、金属粒子が凝集することを抑制できる。 For this reason, for example, when the coating layer 20 covers the surface of the metal core 10, heating can be terminated before the coating layer 20 and the metal core 10 are alloyed. Therefore, even when there is no material that acts as the dispersant 30 for the metal core 10, the use of the material that acts as the dispersant for the coating layer 20 can suppress the aggregation of the metal particles.
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）
まず、還流器がついたガラス製の三口フラスコに、鉄アセチルアセトネート１．４ｍｍｏｌ、白金アセチルアセトネート０．６ｍｍｏｌ、オレイン酸１０ｍｍｏｌ、オレイルアミン １０ｍｍｏｌを加えて混合した。次いで、フラスコ内をアルゴンで置換した後、加熱を開始した。そしてフラスコ内の温度が１４０℃になったときに、１，２−ヘキサデカンジオールを加えた。その後、図４に示すように、フラスコをさらに加熱して３００℃にして、この温度に維持した。加熱を開始した後、フラスコ内から排気される排気ガスに含まれる有機物の濃度を測定し、有機物の濃度が減少し始めてから１０分後にフラスコ内を急冷した。その後、生成した金属粒子を分離し、この金属粒子を６０％の過塩素酸水溶液で処理した。
(Example)
First, 1.4 mmol of iron acetylacetonate, 0.6 mmol of platinum acetylacetonate, 10 mmol of oleic acid, and 10 mmol of oleylamine were added to a glass three-necked flask equipped with a refluxer and mixed. Next, after the inside of the flask was replaced with argon, heating was started. When the temperature in the flask reached 140 ° C., 1,2-hexadecanediol was added. Thereafter, as shown in FIG. 4, the flask was further heated to 300 ° C. and maintained at this temperature. After starting the heating, the concentration of the organic matter contained in the exhaust gas exhausted from the flask was measured, and 10 minutes after the concentration of the organic matter began to decrease, the flask was rapidly cooled. Thereafter, the generated metal particles were separated, and the metal particles were treated with a 60% perchloric acid aqueous solution.
また比較例として、図４に示すように、フラスコを１時間３００℃に維持した。 As a comparative example, as shown in FIG. 4, the flask was maintained at 300 ° C. for 1 hour.
図５（ａ）は、比較例に係る金属粒子の透過型電子顕微鏡写真（ＴＥＭ）であり、図５（ｂ）は実施例に係る金属粒子のうち過塩素酸水溶液で処理する前の金属粒子のＴＥＭ写真である。また図５（ｃ）は、実施例に係る金属粒子のうち過塩素酸水溶液で処理した後の金属粒子のＴＥＭ写真である。 FIG. 5A is a transmission electron micrograph (TEM) of a metal particle according to a comparative example, and FIG. 5B is a metal particle before being treated with a perchloric acid aqueous solution among the metal particles according to the example. It is a TEM photograph of. Moreover, FIG.5 (c) is a TEM photograph of the metal particle after processing with the perchloric acid aqueous solution among the metal particles which concern on an Example.
図５（ｂ）と図５（ａ）を比較して分かるように、実施例に係る金属粒子は、過塩素酸で処理する前においては比較例に係る金属粒子より球から離れた形状をしている。これらのＴＥＭ写真を画像処理ソフトで処理した結果、金属粒子の粒径の変動係数（標準偏差/平均粒子径：ＣＶ）は、実施例においては１８％であったのに対して比較例では１２％であった。これは、被覆層の有無に起因するものと考えられる。 As can be seen by comparing FIG. 5 (b) and FIG. 5 (a), the metal particles according to the example had a shape farther from the sphere than the metal particles according to the comparative example before being treated with perchloric acid. ing. As a result of processing these TEM photographs with image processing software, the coefficient of variation (standard deviation / average particle diameter: CV) of the particle size of the metal particles was 18% in the example, while 12 in the comparative example. %Met. This is considered due to the presence or absence of the coating layer.
また図５（ｃ）に示したＴＥＭ写真を画像処理ソフトで処理した結果、過塩素酸水溶液で処理した後の金属粒子のＣＶは、１６％であり、過塩素酸水溶液で処理する前の値より小さくなった。これは、被覆層が除去されたためと考えられる。 In addition, as a result of processing the TEM photograph shown in FIG. 5C with image processing software, the CV of the metal particles after processing with the perchloric acid aqueous solution is 16%, which is the value before processing with the perchloric acid aqueous solution. It became smaller. This is considered because the coating layer was removed.
図６（ａ）は比較例に係る金属粒子のＸ線回折チャートであり、図６（ｂ）は実施例に係る金属粒子のＸ線回折チャートである。比較例に係るＸ線回折チャートのピークは、Ｆｅ−Ｐｔの合金に起因したピークと略重なっているが、実施例に係るＸ線回折チャートのピークは、Ｆｅ−Ｐｔの合金に起因したピークとＰｔに起因したピークの間に位置している。 FIG. 6A is an X-ray diffraction chart of metal particles according to a comparative example, and FIG. 6B is an X-ray diffraction chart of metal particles according to the example. The peak of the X-ray diffraction chart according to the comparative example substantially overlaps with the peak due to the Fe—Pt alloy, but the peak of the X-ray diffraction chart according to the example is the peak due to the Fe—Pt alloy. Located between peaks due to Pt.
また、実施例に係る金属粒子の組成を蛍光エックス線測定で分析した結果、Ｆｅ：Ｐｔ＝５５：４５であった。一方、比較例に係る金属粒子の組成を傾向エックス線測定で分析した結果、Ｆｅ：Ｐｔ＝４７：５３であった。 Moreover, as a result of analyzing the composition of the metal particle which concerns on an Example by a fluorescent X ray measurement, it was Fe: Pt = 55: 45. On the other hand, as a result of analyzing the composition of the metal particles according to the comparative example by tendency X-ray measurement, it was Fe: Pt = 47: 53.
このように、実施例に係る金属粒子は、比較例に係る金属粒子よりも、鉄の含有率が高いにもかかわらずＸ線回折チャートのピークが鉄白金に起因したピークより白金に起因したピークに近かった。これは、実施例に係る金属粒子において、白金と鉄が固溶せず、粒子表面が、鉄を含む被覆層によって被覆されているためと考えられる。 Thus, although the metal particle which concerns on an Example has the iron content rate higher than the metal particle which concerns on a comparative example, the peak of an X-ray-diffraction chart is a peak which originated in platinum from the peak which originated in iron platinum. It was close to. This is presumably because platinum and iron are not dissolved in the metal particles according to the example, and the particle surface is covered with a coating layer containing iron.
１０ 金属核
２０ 被覆層
３０ 分散剤
１００ 反応容器
１０２ ガス導入管
１０４ 排気管
１２０ 加熱部
１４０ ガス分析部
１６０ 制御部
DESCRIPTION OF SYMBOLS 10 Metal nucleus 20 Coating layer 30 Dispersant 100 Reaction container 102 Gas introduction pipe 104 Exhaust pipe 120 Heating part 140 Gas analysis part 160 Control part
Claims (8)
前記溶媒の中で生じる前記第１の金属化合物及び前記第２の金属化合物の還元反応で生成する副生成物の量の経時変化を測定することにより、前記熱処理の終了タイミングを判断する、金属粒子の製造方法。 Introducing a reducing agent into a solvent containing a first metal compound containing a first metal and a second metal compound containing a second metal, heat-treating,
Metal particles for determining the end timing of the heat treatment by measuring the change over time in the amount of by-products generated in the reduction reaction of the first metal compound and the second metal compound generated in the solvent Manufacturing method.
前記第２の金属化合物は、前記第１の金属化合物より還元しにくい金属粒子の製造方法。 In the manufacturing method of the metal particle of Claim 1,
The method for producing metal particles, wherein the second metal compound is less likely to be reduced than the first metal compound.
前記熱処理の終了タイミングは、前記副生成物の量の最大値を検出してから予め定められた時間が経過した後であり、
前記金属粒子は、
前記第１の金属を含む金属核と、
前記金属核の表面に形成され、前記第２の金属を含んでいて前記第１の金属を含んでいない被覆層と、
を有している金属粒子の製造方法。 In the manufacturing method of the metal particle of Claim 2,
The end timing of the heat treatment is after a predetermined time has elapsed since the maximum amount of the by-product was detected,
The metal particles are
A metal nucleus containing the first metal;
A coating layer formed on the surface of the metal core and containing the second metal and not the first metal;
The manufacturing method of the metal particle which has.
前記熱処理を終了させた後に、前記被覆層を溶かす薬液を用いて、前記金属粒子の前記被覆層を除去する金属粒子の製造方法。 In the manufacturing method of the metal particle of Claim 3,
A method for producing metal particles, wherein after the heat treatment is finished, the coating layer of the metal particles is removed using a chemical solution that dissolves the coating layer.
前記第１の金属化合物及び前記第２の金属化合物は有機金属であり、
前記副生成物は有機物である金属粒子の製造方法。 In the manufacturing method of the metal particle as described in any one of Claims 1-4,
The first metal compound and the second metal compound are organometallic;
The method for producing metal particles, wherein the by-product is an organic substance.
前記副生成物の量を半導体センサー又は赤外吸光により検出する、金属粒子の製造方法。 In the manufacturing method of the metal particle of Claim 5,
A method for producing metal particles, wherein the amount of the by-product is detected by a semiconductor sensor or infrared absorption.
第１の金属を含む金属核と、
前記金属核の表面に形成され、第２の金属を含んでいて前記第１の金属を含んでいない被覆層と、
を有している金属粒子。 Manufactured by the method of claim 1,
A metal nucleus comprising a first metal;
A coating layer formed on a surface of the metal core and including a second metal and not including the first metal;
Having metal particles.
前記反応容器を加熱する加熱部と、
前記反応容器内の雰囲気を分析し、前記第１の金属化合物及び前記第２の金属化合物の還元反応で生成する副生成物の量の経時変化を測定する分析部と、
前記分析部が前記副生成物の量の最大値を検出してから、予め定められた時間が経過した後に前記加熱部による加熱を止める制御部と、
を備える金属粒子製造装置。 A reaction vessel into which a first metal compound containing a first metal, a second metal compound containing a second metal, a solvent, and a reducing agent are introduced;
A heating unit for heating the reaction vessel;
An analysis unit that analyzes the atmosphere in the reaction vessel and measures a change over time in the amount of by-products generated in the reduction reaction of the first metal compound and the second metal compound;
A control unit that stops heating by the heating unit after a predetermined time has elapsed since the analysis unit detected the maximum amount of the by-product;
A metal particle manufacturing apparatus comprising:
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| JPH05126391A (en) * | 1991-11-07 | 1993-05-21 | Daikin Ind Ltd | Operation controller for air conditioner |
| JPH09508887A (en) * | 1994-02-15 | 1997-09-09 | ザ・ダウ・ケミカル・カンパニー | Method for producing metal carbide powder |
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