WO2013118860A1 - 金属コロイド溶液及びその製造方法 - Google Patents
金属コロイド溶液及びその製造方法 Download PDFInfo
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- WO2013118860A1 WO2013118860A1 PCT/JP2013/053029 JP2013053029W WO2013118860A1 WO 2013118860 A1 WO2013118860 A1 WO 2013118860A1 JP 2013053029 W JP2013053029 W JP 2013053029W WO 2013118860 A1 WO2013118860 A1 WO 2013118860A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0039—Post treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0043—Preparation of sols containing elemental metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
- B22F1/147—Making a dispersion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Definitions
- the present invention relates to a metal colloid solution, and more particularly, to a metal colloid solution that is excellent in stability and in which metal ions are not easily eluted from colloid particles over a long period of time.
- a metal colloid is a state in which fine particles (cluster particles) of 1 to 100 nm metal insoluble in a solvent are dispersed and suspended in a solvent, and the form of a metal colloid solution dispersed in a liquid solvent is generally known. ing.
- the metal colloid is used in the above-mentioned applications because the fine particles can be bonded to an arbitrary support in a suitable dispersion state. For example, in the catalyst field, control of the particle size of the catalyst metal on the support is an issue in order to improve activity and ensure durability, but this requirement can be met by using a metal colloid.
- the metal colloid is suitable as a precursor of various materials is that the alloy particles made of a plurality of metals can be bonded to the support while adjusting the composition.
- the metal colloid is easy to adjust the composition of the metal particles in the production process and can be supported on the carrier as it is, so that there is an advantage that catalyst particles having a desired composition can be formed. .
- a process of dissolving a metal compound (metal salt) constituting metal particles in a solvent and adding a reducing agent and a protective agent to the solution is common.
- the metal salt dissolved in the solvent becomes a metal ion, which is reduced by the reducing agent to become a metal atom and aggregates to form cluster particles, and the protective agent binds there to form colloidal particles.
- the protective agent is a compound that can be chemically or physically bonded to the periphery of the cluster particle and physically suppresses and stabilizes the aggregation of the nanoparticles (hereinafter referred to as the cluster particle and the protective agent). Particles bonded to the material are called colloidal particles).
- colloidal particles having a target composition can be produced by using metal salts of constituent metals simultaneously or step by step in consideration of the target composition.
- the colloidal particles are in a stable state by the action of the protective agent and are dispersed in the solvent while maintaining the metal content in the colloidal particles.
- the conventional metal colloid solution undergoes a change with time in the colloidal particles, and its metal content changes slightly.
- the present inventors considered that the metal in the colloidal particles is eluted (reionized) as a factor of the temporal change of the colloidal particles. Such a problem of change of colloidal particles with time has not been pointed out so far.
- the metal ions eluted from the colloidal particles and re-adsorbed may not be regarded as a problem because they are not themselves impurities.
- the metal ions adsorbed on the protective agent as described above are adsorbed on the carrier together with the colloidal particles during the production of the catalyst or the like, and form metal particles different from the colloidal particles. Since the metal particles derived from the metal ions have a particle size different from that of the metal particles formed from the colloidal particles, the particle size distribution of the metal particles on the carrier may be affected.
- the constituent metals are not necessarily dissolved uniformly, so that the compositional variation of the colloidal particles occurs due to elution of metal ions, and the metal particles that exhibit the designed performance cannot be formed.
- the present invention has been made under the above-mentioned problems, and provides a metal colloid solution in which stability, particularly, a change with time of colloidal particles due to elution of metal ions is suppressed.
- a method for producing the metal colloid solution is also disclosed.
- the inventors of the present invention have examined the cause of metal ion elution from colloidal particles. As a result, it was thought to be due to the influence of anions derived from metal salts used in the production of metal colloid solutions. That is, in metal colloid production, metal salts such as chlorides and nitrates are often used. When these metal salts are dissolved in a solvent, chloride ions (Cl ⁇ ), nitrate ions (NO Anions such as 3 ⁇ ) are generated. Thereafter, by adding a reducing agent and a protective agent, the metal ions are reduced to form metal particles, but the anions remain in the solution as they are.
- the present inventors considered that the residual anion dissolves the metal particles of the colloidal particles and reionizes them, so that the metal concentration variation of the colloidal solution and the alloy composition variation occur.
- the elution of the metal ions does not have a fast reaction rate, but proceeds with time as long as anions are present. Therefore, the present inventors have conceived a metal colloid solution that can solve the above-mentioned problems, in which the concentration of these anions is limited to a predetermined value or less.
- the present invention is a metal colloid solution containing colloidal particles composed of metal particles composed of one or more metals and a protective agent that binds to the metal particles, and a solvent that is a dispersion medium for the colloidal particles.
- the metal colloid solution has a chloride ion concentration of 25 ppm or less per 1% by mass of metal concentration and a nitrate ion concentration of 7500 ppm or less per 1% by mass of metal concentration.
- the concentration of chloride ions and nitrate ions is controlled in order to suppress dissolution of metal particles and prevent changes in the metal concentration and alloy composition of the metal colloid solution over time.
- metal salts for the production of colloidal metal solutions chlorides and nitrates are most commonly used. By controlling both chloride ions and nitrate ions derived from these metal salts, good stability is achieved. Metal colloidal solution.
- the upper limit value of chloride ion concentration and the upper limit value of nitrate ion are different because the influence (solubility) of these anions on the metal is different.
- nitrate ions are not as soluble as chloride ions.
- the metal concentration in the metal colloid solution was used as a reference because the production amount of chloride ions etc. changed with the amount of raw material used, the amount of raw material It is considered that the change of also affects the metal concentration.
- chloride ions when starting from chloride are 10000 ppm or more and 5500 ppm or more, respectively. Chloride ions are formed. In the present invention, these are restricted to 25 ppm or less.
- nitrate ions when a platinum colloid solution and a palladium colloid solution having a metal concentration of 1% by mass are used as nitrate (dinitrodiamine platinum, dinitrodiamine palladium) raw materials generate nitrate ions of 15000 ppm or more and 19000 ppm or more, respectively. In the present invention, these are restricted to 7500 ppm or less.
- both chloride ions and nitrate ions may exist, and in this case, it is necessary to fall below the reference value of both.
- chloride ions and nitrate ions exist after colloid production, so the total concentration of platinum concentration and palladium concentration As a reference, the chloride ion concentration is 25 ppm or less and the nitrate ion concentration is 7500 ppm or less.
- the metal colloid solution according to the present invention is the same as the conventional metal colloid except that the anion concentration is regulated.
- the metal particles constituting the colloidal particles are preferably any one of platinum, palladium, rhodium, ruthenium, gold, silver and iridium because of the above-mentioned uses. It is also suitable for alloys of these metals.
- PVP polyvinylpyrrolidone
- the amount of the protective agent is not particularly limited only from the viewpoint of the stability of the metal colloid solution.
- the adsorption characteristics may be emphasized.
- colloidal particles are supported by impregnating a metal colloid solution with an inorganic oxide (alumina, ceria, etc.) as a carrier. At this time, if the adsorbing ability of the colloidal particles is insufficient, the carrier is not supported. In such applications, the ability to adsorb colloidal particles is important.
- the amount of the protective agent is preferably 0.2 to 2.5 times the mass of the metal particles, as long as the adsorbability can be secured under a relatively wide range of loading conditions (inorganic oxide types, etc.). . If the amount of the protective agent exceeds 2.5 times, the amount of the protective agent is too large even if other supporting conditions are adjusted, and the adsorption ability of the colloidal particles is lowered due to steric hindrance. Further, the amount of the protective agent less than 0.2 times affects the stability of the colloidal particles, and there is a risk of aggregation of the metal particles in the metal colloid solution and a risk of ionization of the metal particles.
- the amount of the protective agent is more preferably 0.2 to 2.0 times.
- the amount of the protective agent is often set to 3.0 times or more. This is considered to be due to the idea that it is appropriate to use an equal amount or more of the protective agent with respect to the metal, placing importance on the action of the protective agent having steric repulsion.
- the metal concentration in the metal colloid solution is preferably 0.01 to 8.00% by mass.
- a dilute metal colloid solution may be produced for the purpose of emphasizing stability during production, and the metal concentration may be increased by concentrating the solution.
- Particularly preferred is 0.1 to 4%.
- the colloidal metal solution according to the present invention tends to set the amount of the protective agent low in order to eliminate the steric hindrance of the protective agent and improve the adsorption ability of the colloidal particles.
- the stability of the colloidal particles is not hindered by setting a lower amount of the protective agent.
- the metal colloid solution according to the present invention can ensure the stability of the solution by additionally having a protective agent that does not bind to the metal.
- the thus added protective agent acts as a buffer material for preventing aggregation without being bound to the colloidal particles even in the metal colloid solution.
- the amount of the protective agent additionally present in the metal colloid solution is such that the amount of the protective agent that binds to the metal in the colloidal particles is 0.2 to 2.5 times the mass of the metal particles as described above. When it is (more preferably 0.2 to 2.0 times), the protective agent that does not bind to the metal particles is preferably 0.1 to 2.8 times the mass of the metal particles.
- the metal colloid solution to which the protective agent is added in this way can be used for catalyst production and the like.
- the production method according to the present invention is based on the process of forming colloidal particles by adding one or more metal salts, a protective agent, and a reducing agent to a solvent, and so far the same as the conventional method for producing a metal colloid solution. However, it is characterized in that it includes a removal step (demineralization treatment, denitration treatment: hereinafter referred to as a stabilization treatment step) for reducing the concentration of chloride ions and the like.
- a removal step demineralization treatment, denitration treatment: hereinafter referred to as a stabilization treatment step
- the colloidal particle forming step will be described in detail.
- the colloidal particle forming step is a step of reducing a metal ion in a solvent and binding a protective agent to the metal particle.
- a solvent water is suitable, but an organic solvent or a mixed solvent of water and an organic solvent can also be applied.
- the metal salt used as the raw material for the metal colloid includes hexachloroplatinic acid, dinitrodiammine platinum, dinitrodiammine platinum nitrate, platinum chloride (first and second), chloroplatinic acid, Chloroplatinate and the like can be applied.
- a metal salt for producing a palladium colloid palladium chloride, palladium nitrate, dinitrodiamine palladium and the like can be applied.
- metal salts for producing gold colloids chloroauric acid, chloroaurate, and the like can be applied.
- a metal salt for producing a silver colloid silver chlorate, silver nitrate or the like can be applied.
- a metal salt for producing a ruthenium colloid ruthenium chloride and ruthenium nitrate can be applied.
- Rhodium chloride, rhodium nitrate, or the like can be used as a metal salt for producing a rhodium colloid.
- the metal salt for producing the iridium colloid hexachloroiridium acid, iridium trichloride and the like can be applied. Further, when a multi-component metal alloy colloid composed of a plurality of metals is produced, it can be produced by simultaneously dissolving the metal salt in a solvent.
- the above-mentioned various polymer organic compounds are applied.
- the reducing agent those used in conventional colloid production can be applied.
- alcohols such as formic acid, ethanol, methanol, propanol, and butanol
- glycols such as ethylene glycol, hydrogen, sodium borohydride, hydrazine, dimethylamine borane, and trimethylamine borane can be applied.
- the constituent metals when producing an alloy colloid, the constituent metals may be reduced simultaneously or stepwise.
- both metal salts Pt salt, Pd salt), reducing agent, and protective agent may be mixed in a solvent.
- a metal salt (Pt salt), a reducing agent, and a protective agent may be mixed to form colloidal particles of one metal, and the other metal salt (Pd salt) and a reducing agent may be added thereto to form an alloy. .
- the first is anion removal by ultrafiltration.
- Ultrafiltration is because anions cannot be removed by normal filtration.
- the filtration membrane for ultrafiltration preferably has a molecular weight cut-off of 5000 to 40000.
- the second step of the stabilization treatment step is to add alkali to the solution after colloidal particle formation.
- This alkali addition reduces the total concentration of chloride ions and the like by neutralizing chloride ions and forming salts.
- the alkali to be added is preferably ammonia, sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium carbonate, lithium carbonate, potassium carbonate, calcium hydroxide, or hydroxytetramethylammonium.
- the amount of alkali added can be determined by calculating the total amount of chloride ions and nitrate ions contained in the metal salt used in the production of the metal colloid solution.
- the solution after addition of alkali can be used as it is as a metal colloid solution.
- the colloidal particles can be collected by filtration and re-dispersed in a solvent to obtain a metal colloid solution.
- a step of centrifuging the metal colloid solution to cause precipitation and decanting the metal colloid solution can be applied.
- the conditions for this centrifugation step are that the colloidal metal particles are precipitated by rotating the metal colloid solution at a rotational speed of 5000 to 8000 rpm for 5 to 10 minutes, and the supernatant is removed from the system while leaving the precipitate.
- a metal colloidal solution can be obtained by adjusting the concentration while redispersing the colloidal particles by adding a solvent.
- the decomposition and removal process is also useful as an effective method for removing nitrate ions.
- a method for decomposing nitrate ions various energies of heat, microwaves, ultrasonic waves, and plasma are imparted to the metal colloid solution.
- a metal colloid solution is heated at a temperature close to its boiling point (100 to 120 ° C.) for 4 to 15 hours, and exhausted while boiling, so that nitrate ions in the solution are obtained. Can be decomposed and degassed to reduce the nitrate ion concentration.
- a metal colloid solution with reduced chloride ions and the like can be produced. Further, the colloidal metal solution thus produced may be subjected to a separation operation such as filtration to collect colloidal particles, and may be redispersed in an appropriate solvent to form a colloidal metal solution.
- the colloidal metal solution according to the present invention is stable over a long period of time, and changes in the metal concentration or composition over time are suppressed.
- a functional material such as a catalyst
- a metal / alloy having a metal amount and a raw composition as designed can be fixed to an appropriate support.
- a metal salt solution composed of one or more kinds of metal salts is prepared, and after adding a protective agent solution in which a protective agent is dissolved, a reducing agent is added, and then the mixture is refluxed at 100 ° C. for 2 hours. Was made. And after performing the process which removes a chloride ion or a nitrate ion about this metal colloid solution, the solution after a process was concentrated by heating, and it was set as the metal colloid solution which raised the metal concentration.
- Table 1 shows the metal colloid solutions prepared in this embodiment.
- the colloidal solution is sampled at predetermined intervals (on the day, 1, 7, and 30 days) for the manufactured metal colloid solution, and 100 mL of the solution is put in an ultrafiltration device (fractionated molecular weight). 10000) Pressurized with 4 atmospheres of Ar gas, filtered, ICP analysis of the filtrate, the ratio of eluted metal ions (mass basis of the amount of metal charged) was calculated. The occurrence of precipitation was determined by filtering the sampled solution with a membrane filter having a pore size of 0.2 ⁇ m and whether or not the precipitate remained on the filter paper. The evaluation results are shown in Table 2.
- the amount of the protective agent affects the adsorption performance of the metal colloid.
- the metal colloids of Examples 1 to 13 have a protective agent amount set to 2.0 times or less, and are adsorbed at 100% adsorption rate on all inorganic oxide carriers.
- Comparative Examples 1 to 7 mainly have a relatively large amount of protective agent, and the adsorption rate is low. In Comparative Example 3, the adsorption rate was low although the amount of the protective agent was small. This is probably because precipitation was observed as described above.
- the comparative example 8 also has few protective agents, it is thought that the metal elution amount was large with nitrate ion, and as a result, the adsorption rate was measured low. From the above, it can be seen that, in order to obtain a metal colloid solution having excellent adsorptivity in addition to stability, it is preferable to consider the amount of the protective agent in addition to the reduction of chloride ions and the like in the solution.
- the colloidal metal solution according to the present invention has excellent stability and little change in the metal composition of the colloidal particles even after a long period of time. Moreover, this invention can improve the adsorption capacity with respect to various support
Abstract
Description
a.限外濾過:分画分子量10000の限外濾過フィールターに金属コロイド溶液を通過させて塩化物イオンを除去した。
b.遠心分離:金属コロイド溶液に、メタノールを体積基準で10%分添加した後、回転数6000rpmで5分間遠心分離し、上澄みをデカンテーションして取り除き、沈殿物に水を加えてコロイド濃度を調節した。
c.加熱処理:還元剤添加の行う加熱還流処理後(100℃、2時間)に作製した金属コロイド溶液について、そのまま10時間加熱還流処理を行い、硝酸イオンを分解除去した。
d.アルカリ添加:金属コロイド溶液に、pHメータ測定でpHが5~7になるまでアンモニアを添加した。
Claims (10)
- 1又は2以上の金属からなる金属粒子と前記金属粒子に結合する保護剤とからなるコロイド粒子と、前記コロイド粒子の分散媒である溶媒と、を含む金属コロイド溶液であって、
金属濃度1質量%あたりの塩化物イオン濃度が25ppm以下であり、かつ、金属濃度1質量%あたりの硝酸イオン濃度が7500ppm以下である金属コロイド溶液。 - 金属粒子は、白金、パラジウム、ロジウム、ルテニウム、金、銀、イリジウムのいずれかの金属である請求項1記載の金属コロイド溶液。
- 金属濃度が0.01~8.0質量%である請求項1又は請求項2記載の金属コロイド溶液。
- コロイド粒子の保護剤の量は、金属粒子の質量に対して0.2~2.5倍である請求項1~請求項3のいずれかに記載の金属コロイド溶液。
- 更に、金属粒子と結合しない保護剤が金属粒子の質量に対して0.1~2.8倍含まれたものである請求項4記載の金属コロイド溶液。
- 請求項1~請求項5のいずれかに記載の金属コロイド溶液の製造方法であって、
溶媒に、1種以上の金属塩、保護剤、還元剤を添加することによりコロイド粒子を形成して金属コロイド溶液を製造する工程と、
前記金属コロイド溶液中の塩化物イオン及び/又は硝酸イオンを除去する安定化処理工程とを含む金属コロイド溶液の製造方法。 - 安定化処理工程は、金属コロイド溶液を限外濾過する工程である請求項6記載の金属コロイド溶液の製造方法
- 安定化処理工程は、金属コロイド溶液にアルカリを添加する工程である請求項6記載の金属コロイド溶液の製造方法
- 安定化処理工程は、金属コロイド溶液を遠心分離して沈殿を生じさせ、金属コロイド溶液をデカンテーションする工程である請求項6記載の金属コロイド溶液の製造方法
- 安定化処理工程は、金属コロイド溶液中の硝酸イオンを除去する工程であり、前記金属コロイド溶液に、熱、マイクロ波、超音波、プラズマのエネルギーを付与して、硝酸イオンを分解させる工程である請求項6記載の金属コロイド溶液の製造方法
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US14/370,392 US10220377B2 (en) | 2012-02-09 | 2013-02-08 | Metal colloidal solution and method for producing the same |
EP13747288.2A EP2813303A4 (en) | 2012-02-09 | 2013-02-08 | COLLOIDAL METAL SOLUTION AND PROCESS FOR PRODUCING THE SAME |
CN201380008111.0A CN104105562B (zh) | 2012-02-09 | 2013-02-08 | 金属胶体溶液及其制造方法 |
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JP2020507219A (ja) * | 2017-02-03 | 2020-03-05 | アプライド マテリアルズ インコーポレイテッドApplied Materials,Incorporated | 半導体プロセスの廃水からの亜酸化窒素のプラズマ軽減 |
TWI648099B (zh) * | 2017-06-19 | 2019-01-21 | 健鼎科技股份有限公司 | 金屬奈米粒子膠體溶液的製法 |
JP6973750B2 (ja) * | 2017-11-24 | 2021-12-01 | 株式会社ノリタケカンパニーリミテド | 貴金属ナノ粒子の製造方法 |
TWI670113B (zh) * | 2018-10-15 | 2019-09-01 | 鑫鼎奈米科技股份有限公司 | 製備鉑奈米粒子膠體溶液的方法 |
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Also Published As
Publication number | Publication date |
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CN104105562B (zh) | 2017-02-22 |
JP2013163830A (ja) | 2013-08-22 |
JP5343138B2 (ja) | 2013-11-13 |
TWI569871B (zh) | 2017-02-11 |
ZA201405807B (en) | 2015-11-25 |
EP2813303A4 (en) | 2015-10-07 |
CN104105562A (zh) | 2014-10-15 |
KR101622064B1 (ko) | 2016-05-17 |
TW201343248A (zh) | 2013-11-01 |
EP2813303A1 (en) | 2014-12-17 |
US20140357470A1 (en) | 2014-12-04 |
KR20140121425A (ko) | 2014-10-15 |
US10220377B2 (en) | 2019-03-05 |
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