WO2016136969A1 - Method for producing carrier for fine particles of late transition metal - Google Patents
Method for producing carrier for fine particles of late transition metal Download PDFInfo
- Publication number
- WO2016136969A1 WO2016136969A1 PCT/JP2016/055899 JP2016055899W WO2016136969A1 WO 2016136969 A1 WO2016136969 A1 WO 2016136969A1 JP 2016055899 W JP2016055899 W JP 2016055899W WO 2016136969 A1 WO2016136969 A1 WO 2016136969A1
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- WIPO (PCT)
- Prior art keywords
- complex
- amino acid
- gold
- carrier
- group
- Prior art date
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Images
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- H—ELECTRICITY
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- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a method for producing a carrier in which fine particles of late transition metal such as gold are carried on a carrier.
- Precious metal catalysts have been used for a long time in various fields.
- Gold a precious metal, was once thought to be an inactive element as a catalyst, but in the 1980's, gold was able to be prepared in the form of fine particles of about 5 nm or less, and its high catalytic activity was discovered.
- research for the application of gold nanoparticle catalysts is being actively conducted.
- the impregnation method is a simple method in which a carrier is immersed in a metal dispersion or solution, dried and then fired, and is suitable for commercial production.
- Non-patent Document 1 a method for preparing a gold nanoparticle carrier by an impregnation method using gold acetate (Patent Document 1) has been reported.
- gold acetate has low solubility in water, and this method requires a plurality of steps for preparing a chloride ion-free impregnation solution.
- An object of the present invention is to provide a novel means that makes it possible to produce a metal fine particle carrier in which metal fine particles such as gold are supported on a carrier by a simple process at a low cost.
- a complex in which an amino acid molecule or an amino acid analog is coordinated to a late transition metal can be prepared from chloroauric acid in a short process, and that this late transition metal / amino acid complex or
- nano-sized particles can be prepared even when gold is used, the late transition metal / amino acid complex, and the late transition metal.
- the amino acid analog compound complex has good solubility in water, and since the amount of the aqueous solvent used in the impregnation step is very small, the amount of waste liquid can be reduced, and the metal fine particle support can be prepared at low cost. The present invention was completed.
- the present invention comprises mixing at least one complex solution selected from the group consisting of late-period transition metal / amino acid complex and late-period transition metal / amino acid analog compound complex with a carrier, and said at least one complex.
- a method for producing a late transition metal fine particle carrier comprising a step of impregnating a carrier with a carrier and a step of firing the carrier after impregnation with a complex is provided.
- the present invention also provides a metal complex in which an amino acid (excluding glycine, histidine, and tryptophan) or an amino acid analog is coordinated to a late transition metal.
- the present invention provides for the first time a method for producing a late transition metal fine particle support by an impregnation method using a complex in which an amino acid or an amino acid analog is coordinated to a late transition metal as a metal precursor.
- the late transition metal / amino acid complex and the late transition metal / amino acid analog compound complex have good solubility in water, and the preparation of the impregnation solution is very simple only by dissolving the complex in a solvent such as water.
- the solubility in water is high, the amount of the solvent used can be reduced, the volume of the impregnating liquid can be reduced, and the amount of the waste liquid can be reduced, which is suitable for mass production at a low cost.
- the impregnation method according to the present invention can also be applied to the preparation of a gold nanoparticle carrier. Furthermore, according to the method of the present invention, even an acidic carrier that is usually difficult to use can be used. Therefore, a metal particle carrier having a very small size is prepared using various carriers, regardless of the type of the carrier. be able to.
- Gold / glycine complex impregnation method using (standard condition) Au supported silica prepared by (1 wt% Au / SiO 2 - (G-3)) is a result of DMTS examining the adsorption capacity.
- Gold / glycine complex impregnation method using (baking time 30 changes in minutes) Au supported silica prepared by (1 wt% Au / SiO 2 - (G-7)) is the result of DMTS examining the adsorption capacity.
- Gold / glycine complex impregnation method using Au supported silica prepared by (change the firing temperature to 200 °C) (1 wt% Au / SiO 2 - (G-8)) is a result of DMTS examining the adsorption capacity. It is the result of investigating the DMTS adsorption capacity of a commercially available Au-supported silica catalyst (1 wt% Au / SiO 2- (H)).
- DMTS adsorption ability of Au-supported silica (1 wt% Au / SiO 2- (G-1)) prepared by impregnation method using gold / glycine complex (using 10 mL of water for dissolution and evaporation drying) was investigated. It is a result.
- Au supported silica was prepared by impregnation method using (1 wt% Au / SiO 2 - (GABA)) is the result of DMTS examining the adsorption capacity.
- Au-supported aluminum-containing mesoporous silica (1 ⁇ wt% Au / Al-MCM-41- (A)) in which gold particles are impregnated and supported on an aluminum-containing mesoporous silica (Al-MCM41) support using a gold / ⁇ -alanine complex It is the result of investigating the DMTS adsorption ability.
- a late transition metal / amino acid complex in which an amino acid is coordinated to a late transition metal and an amino acid analog compound to a late transition metal are coordinated It is characterized by using at least one selected from the group consisting of a periodic transition metal / amino acid analog compound complex.
- amino acids and amino acid analogs may be collectively referred to as “amino acid compounds”.
- the late transition metals include gold, silver, platinum, palladium, ruthenium, rhodium, osmium, iridium, iron, cobalt, nickel, copper, zinc and lead, and at least one of these metals.
- Species can be used.
- examples of metals that can be preferably used include at least one selected from the group consisting of gold, silver, platinum, and palladium, in particular, gold, but are not limited thereto.
- amino acid coordinated to the metal is not particularly limited.
- an “amino acid” refers to a compound having an amino group and a carboxy group in the molecule. As defined in general amino acids, the amino group hydrogen is substituted for other parts in the molecule. Also included are imino acids, which are cyclic compounds that have been converted to secondary amines. Representative examples of amino acids that can be used in the present invention include, but are not limited to, 20 ⁇ -amino acids constituting natural proteins, and ⁇ -, ⁇ -, and ⁇ -amino acids are also included. . The amino acid may be D-form or L-form, or a mixture of both.
- amino acids include arginine, histidine, lysine, aspartic acid, glutamic acid, alanine, glycine, leucine, valine, isoleucine, serine, threonine, phenylalanine, tryptophan, tyrosine, cystine or cysteine, glutamine, asparagine, proline, methionine.
- amino acid analog compound is not particularly limited as long as it has a structure similar to an amino acid as defined above.
- amino acid analogs include A compound in which at least one (for example, all or one or two, or one) amino group of an amino acid molecule is replaced with a sulfhydryl group; A compound in which at least one alkyl group is bonded to at least one (for example, all, one, two, or one) amino group of an amino acid molecule (the carbon number of the alkyl group is, for example, 1 to 5, 1 to 4, 1 to 3, 1 or 2, or 1); At least one (for example, 1 to 5, or 1 to 3, or 1 or 2, or 1) carbon atoms constituting the main chain and side chain of the amino acid molecule are a nitrogen atom, an oxygen atom, and a sulfur atom.
- a compound substituted with at least one selected from: and at least one of carbon atoms constituting the main chain and side chain of the amino acid molecule eg, 1 to 5, 1 to 4, 1 to 3, 1 or A compound in which at least one selected from the group consisting of an alkyl group, a hydroxyl group and a halogen atom is bonded to two or one (the number of carbons in the alkyl group is, for example, 1 to 5, 1 to 4, 1 to 3) Piece, one piece, two pieces, or one piece) Etc.
- amino acid analogs include thiomalic acid (aspartic acid analog in which the —NH 2 group of aspartic acid is replaced with —SH group), p-chlorophenylalanine (phenylalanine in which the para position of the phenyl group is substituted with a chlorine atom) Similar compounds), ⁇ -chloroalanine (Alanine analogs in which the ⁇ carbon is replaced by chlorine atoms), hydroxyproline (hydroxylated proline, collagen component), hydroxylysine (hydroxylated lysine, collagen component) Sarcosine (N-methylglycine, a glycine-like compound in which one methyl group is bonded to the amino group of glycine), and the like, but is not limited thereto.
- the type of the carrier is not particularly limited, and any carrier can be used as long as it can carry the late transition metal in the form of nano-sized particles or less on the surface thereof. According to the method of the present invention, it is possible to use an acidic carrier which is difficult to use by a normal impregnation method.
- Specific examples of the carrier include silicon materials (silica, silica-alumina, aluminosilicate, etc.), carbon materials (activated carbon, various porous carbon materials, etc.), metal oxides (iron oxide, aluminum oxide, titanium oxide).
- PCP Porous Coordination Polymer
- PCP metal ions and those A crystalline polymer structure composed of a bridging organic ligand Ri, metal organic structures; also referred to
- the shape of the carrier is not particularly limited, and may be any shape / form. For example, various shapes such as powder, granules, pellets, and honeycombs can be used.
- the specific surface area of the carrier is not particularly limited, but usually a porous carrier having a large specific surface area (for example, about 30 m 2 / g or more, particularly about 100 m 2 / g or more) is preferably used.
- the upper limit of the specific surface area is not particularly limited, but is usually about 3000 m 2 / g or less.
- an amino acid compound is dissolved in a basic alcohol aqueous solvent, an alcohol aqueous solution of a late transition metal soluble compound is added thereto, and an alcohol is further added to precipitate a complex, which is recovered.
- an appropriate alcohol By washing after reprecipitation with an appropriate alcohol, a late transition metal / amino acid compound complex can be obtained.
- a lower alcohol such as ethanol may be used as the alcohol.
- late transition metal soluble compounds include chloroauric acid in the case of gold; chloroplatinic acid and platinum nitrate in the case of platinum; silver nitrate in the case of silver; palladium chloride and palladium nitrate in the case of palladium. be able to.
- the impregnation support on the carrier of the late transition metal / amino acid compound complex may be carried out by dissolving the complex in water, adding the carrier to this, stirring and mixing, and firing. Complexes with different coordinated amino acid compounds may be mixed and impregnated into the carrier.
- the size of the metal fine particles on the carrier is reduced by reducing the amount of water used to dissolve the complex as much as possible, stirring and mixing the carrier and the complex aqueous solution, impregnating the carrier with the complex, and immediately subjecting it to firing without drying. It has been confirmed by experiments using gold that can be reduced to about 10 nm or less.
- metal particles having a slightly larger average particle diameter about 10 nm to 30 nm
- the stirring and mixing time with the carrier is not particularly limited, and a few minutes to several tens of minutes is sufficient.
- the firing temperature may be about 100 ° C. to 600 ° C., for example, about 150 ° C. to 400 ° C.
- the firing time may be about several minutes to over a dozen hours, for example, about 20 minutes to 10 hours.
- Firing may be performed in an oxygen-containing atmosphere such as air, or may be performed in a reducing gas atmosphere or an inert gas atmosphere. Since the amino acid compound contained in the complex disappears due to the calcination treatment, there is no concern that unnecessary components that lower the performance such as catalytic activity remain on the support.
- the present invention it is possible to obtain a metal fine particle carrier in which late-period transition metal fine particles having an average particle size of about 50 nm or less are supported on a carrier.
- particle size and particle size of the metal fine particles supported on the carrier refer to the diameter of the metal fine particles which are substantially hemispherical and fixed on the carrier.
- the size of the metal fine particles can be adjusted by adjusting the production conditions within the range of the above-described conditions.
- the impregnation support may be carried out under conditions such as firing without drying.
- the size of the metal fine particles supported on the carrier can also be reduced by using a late transition metal / amino acid compound complex having a particularly high solubility in water.
- the lower limit of the size of the metal fine particles on the support obtained by the method of the present invention is not particularly limited, but is usually an average particle size of 0.5 nm or more, for example, an average particle size of about 1 nm or more.
- the late transition metal fine particle carrier obtained by the production method of the present invention usually has a metal loading of about 0.1 to 30 wt%.
- the late transition metal fine particle carrier produced by the method of the present invention can be used as a catalyst in the same manner as various types of noble metal catalysts known in the art.
- known gold nanoparticle catalysts catalyze various reactions such as decomposition of harmful components in the environment, fuel cell-related reactions (anodic reactions, etc.), chemical process reactions such as propylene, styrene gas phase epoxidation, etc.
- the gold fine particle carrier produced by using the gold / amino acid compound complex by the method of the present invention can also be used as a catalyst for various reactions in the same manner as the known gold nanoparticle catalyst.
- adsorbents Besides the catalyst, application to adsorbents, mechanical materials, optical materials, electromagnetic materials, etc. is also possible.
- gold fine particles are known to have an action of adsorbing sulfur compounds (Japanese Patent No. 5170591), and gold fine particle carriers produced by the method of the present invention can also be used as sulfur compound adsorbents. it can.
- polysulfides such as dimethyl trisulfide and dimethyl disulfide are the main constituents of Oika, which is a deteriorated odor of sake (Japan Brewing Association, 101, 125-131, 2006). Can be used as a polysulfide adsorption / removal agent for the reduction of scent in sake.
- the late transition metal fine particle carrier produced by the method of the present invention is not only used for adsorption removal of sulfur compounds from aqueous liquids, but also for liquid fuels such as gasoline, as in the invention described in Japanese Patent No. 5170591. It can also be used as an adsorbent for adsorbing and removing sulfur compounds from lipophilic liquids such as organic solvents.
- Impregnation of gold on the support 15 mg of gold / glycine complex is placed in a mortar and 0.5 mL of water is added and dissolved, and then 990 mg of SiO 2 (Fuji Silysia Chemical, CARiACT Q-15, specific surface area 200 m 2 / g) was added and mixed with stirring for 30 minutes. Thereafter, air baking (300 ° C., 4 hours) was immediately performed without drying, and gold particles were supported on SiO 2 .
- gold particles having a small size of about 5 nm or less could be prepared under the conditions [1] to [3], [6] to [8], and [10].
- the condition [9] large specific surface area of the silica support
- the DR method slightly larger gold particles of about 10 nm or more were prepared.
- amino acids include ⁇ -alanine, 4-aminobutyric acid, lysine, asparagine, D, L-alanine, 5-aminovaleric acid, 6-aminocaproic acid, methionine, glutamic acid, histidine, and tryptophan.
- thiomalic acid was used as an amino acid analog. In a beaker, 2.5 mmol of sodium hydroxide and 2.5 mmol of an amino acid compound were dissolved in 2 mL of water, and 3 mL of ethanol was added.
- a gold / amino acid compound complex (equivalent to 10 mg of gold) was placed in a mortar, dissolved by adding 0.5 mL of water, 990 mg of SiO 2 was added thereto, and the mixture was stirred and mixed for 30 minutes. Thereafter, air baking was performed at 300 ° C. for 4 hours without drying.
- Examples of the results of XRD measurement of Au-supported silica (Au / SiO 2 ) prepared using various gold / amino acid compound complexes include ⁇ -alanine (Preparation Example 1), 4-aminobutyric acid (Preparation Example 1), FIG. 1 shows the result of XRD measurement of Au / SiO 2 using a complex of lysine or asparagine (Preparation Example 1) and gold.
- Table 2 shows the particle diameters of Au-supported silica (Au / SiO 2 ) prepared using various gold / amino acid compound complexes with a gold peak near 38 °. In either case, gold particles having a small particle size could be prepared.
- the centrifugally washed gold / ⁇ -alanine complex was dissolved in water, mixed with SiO 2 , vacuum lyophilized, and then air baked.
- the particle size was 9.1 nm as measured by XRD. It was reconfirmed that in order to prepare gold particles having a small particle size, it was necessary not to dry, since the particle size was increased by drying after mixing with SiO 2 .
- ⁇ Aluminum-containing mesoporous silica support> Place gold / amino acid complex (equivalent to 10 mg of gold) in a mortar, add 0.5 mL of water to dissolve, add 990 mg of silica alumina (aluminum-containing mesoporous silica MCM-41, Sigma-Aldrich), and stir and mix for 30 minutes. did. Thereafter, air calcination was carried out at 300 ° C. for 4 hours without drying to obtain Au-supported aluminum-containing mesoporous silica (Au / Al-MCM-41- (A)).
- the average particle diameter of the gold particles calculated from the transmission electron microscope (TEM) image was 2.5 nm, and gold particles having a small particle diameter could be supported as in the case of the silica carrier.
- ⁇ Activated carbon carrier> A gold / ⁇ -alanine complex (equivalent to 5 mg of gold) was placed in a mortar, 0.5 mL of water was added and stirred, 495 mg of activated carbon (Ketjen Black, Lion Co., Ltd.) was added, and the mixture was stirred and mixed for 30 minutes. Thereafter, air baking was performed at 300 ° C. for 30 minutes without drying to obtain Au-supported activated carbon (Au / C- (A)). The size of the gold particles supported on the activated carbon support was 4.7 nm, and gold particles having a small particle diameter could be supported as in the case of the silica support.
- ⁇ Montmorillonite carrier> A gold / amino acid complex (equivalent to 10 mg of gold) was placed in a mortar, dissolved by adding 0.5 mL of water, 990 mg of montmorillonite (Sigma Aldrich) was added thereto, and the mixture was stirred and mixed for 30 minutes. Thereafter, air baking was performed at 300 ° C. for 4 hours without drying.
- the gold particle size of the obtained Au-supported montmorillonite (Au / Mont) is about 10 nm (calculated from a transmission electron microscope (TEM) image). Gold particles having a small diameter could be supported.
- DMTS adsorption experiment using gold fine particle carrier-1 As one use of the metal fine particle carrier prepared by the method of the present invention, dimethyl trisulfide, which is an aroma component of sake using the various gold fine particle carriers prepared above, assuming an adsorption / removal agent for sulfur-containing compounds. (DMTS) (Japan Brewing Association Journal, 101, 125-131, 2006) was subjected to an adsorption experiment.
- DMTS adsorption experiment using gold fine particle support-2 As a further example of the use of the fine metal particle support prepared by the method of the present invention, it is assumed that the sulfur-containing compound is adsorbed and removed from a liquid fuel such as gasoline and an oleophilic liquid such as an organic solvent. Was used to perform adsorption experiments of DMTS added to hexane.
- Oxide-supported gold catalysts are known to be effective as catalysts for various reactions such as hydrogenation, oxidation, and CC bond formation reactions.
- the prepared gold fine particle support is also considered to be effective as a catalyst for these reactions. Therefore, metal fine particle carriers were prepared by a novel impregnation method using various metal oxides as carriers, and the catalytic activity of their hydrogenation reaction was investigated.
- a gold / ⁇ -alanine complex (equivalent to 40 mg of gold) was placed in a mortar, dissolved by adding 0.5 mL of water, 960 mg of SiO 2 was added thereto, and the mixture was stirred and mixed for 30 minutes. Thereafter, air baking was performed at 300 ° C. for 4 hours without drying.
- ⁇ Titanium oxide carrier> A gold / ⁇ -alanine complex (equivalent to 10 mg of gold) was placed in a mortar, dissolved by adding 0.5 mL of water, 990 mg of titanium oxide (P-25, Nippon Aerosil Co., Ltd.) was added thereto, and the mixture was stirred and mixed for 30 minutes. Thereafter, air baking was performed at 300 ° C. for 4 hours without drying to obtain Au-supported titanium oxide (Au / TiO 2- (A)).
- the average particle diameter of the gold particles calculated from the transmission electron microscope (TEM) image was 2.5 nm, and gold particles having a small particle diameter could be supported as in the case of the silica carrier.
- ⁇ Tungsten oxide carrier> A gold / ⁇ -alanine complex (equivalent to 10 mg of gold) was placed in a mortar, dissolved by adding 0.5 mL of water, 990 mg of tungsten oxide (Wako Pure Chemical Industries, Ltd.) was added thereto, and the mixture was stirred and mixed for 30 minutes. Thereafter, air baking was performed at 300 ° C. for 4 hours without drying to obtain Au-supported tungsten oxide (Au / WO 3- (A)).
- ⁇ Zirconium oxide support> Place a gold / ⁇ -alanine complex (equivalent to 10 mg of gold) in a mortar, add 0.5 mL of water to dissolve it, and dissolve 990 mg of zirconium oxide (Catalyst Society Reference Catalyst (Daiichi Rare Element Chemical Co., Ltd.)) JRC-ZRO-4) was added and mixed with stirring for 30 minutes. Then, air baking was performed at 300 ° C. for 4 hours without drying to obtain Au-supported zirconium oxide (Au / ZrO 2- (A)).
- ⁇ Aluminum oxide carrier> Place a gold / ⁇ -alanine complex (equivalent to 10 mg of gold) in a mortar, add 0.5 mL of water to dissolve it, and dissolve 990 mg of zirconium oxide (Catalyst Society Reference Catalyst (Mizusawa Chemical Co., Ltd.), product number: JRC-ALO -5) was added and mixed with stirring for 30 minutes. Thereafter, air baking was performed at 300 ° C. for 4 hours without drying to obtain Au-supported aluminum oxide (Au / Al 2 O 3- (A)).
- the molecular structure of the gold / ⁇ -alanine complex is a single molecule in which two ⁇ -alanine molecules or one ⁇ -alanine molecule and two hydroxyl groups are coordinated. It was suggested to be a nuclear complex.
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Abstract
Provided is a novel means that makes it possible to use a simple process to inexpensively produce a fine metal particle carrier in which fine metal particles of a metal and the like are loaded on a carrier. This method for producing a carrier for fine particles of a late transition metal includes: a step in which a carrier is mixed with a solution of at least one type of complex selected from the group consisting of late transition metal/amino acid complexes and late transition metal/amino acid-like compound complexes and the carrier is impregnated with the at least one type of complex; and a step in which the complex-impregnated carrier is fired.
Description
本発明は、担体上に金等の後周期遷移金属の微粒子を担持させた担持体の製造方法に関する。
The present invention relates to a method for producing a carrier in which fine particles of late transition metal such as gold are carried on a carrier.
貴金属触媒は様々な分野において古くから活用されている。貴金属のうち金については、かつては触媒としては不活性な元素であると考えられてきたが、1980年代に入って金を5nm程度以下の微粒子状に調製可能になるとともにその高い触媒活性が発見され、現在では金ナノ粒子触媒の応用のための研究が活発に行なわれている。
Precious metal catalysts have been used for a long time in various fields. Gold, a precious metal, was once thought to be an inactive element as a catalyst, but in the 1980's, gold was able to be prepared in the form of fine particles of about 5 nm or less, and its high catalytic activity was discovered. Currently, research for the application of gold nanoparticle catalysts is being actively conducted.
金の微粒子を担体上に担持させた材料の製造方法としては、析出沈殿法、共沈法、析出還元法、ゾル固定化法、固相混合法、気相グラフティング法、含浸法などが知られている。中でも含浸法は、金属の分散液ないしは溶液中に担体を浸漬し、乾燥させた後に焼成するというシンプルな手法であり、商業的生産に適している。
As a method for producing a material in which gold fine particles are supported on a carrier, a precipitation precipitation method, a coprecipitation method, a precipitation reduction method, a sol immobilization method, a solid phase mixing method, a gas phase grafting method, an impregnation method, and the like are known. It has been. In particular, the impregnation method is a simple method in which a carrier is immersed in a metal dispersion or solution, dried and then fired, and is suitable for commercial production.
しかしながら、金微粒子担持体は含浸法による製造が困難である。塩化金酸を用いて含浸法で調製すると、塩化物イオンが金の粒径を大きくしてしまうからである(非特許文献1)。従来、金微粒子触媒の調製は、共沈法や析出沈殿法により行われてきた。近年では、酢酸金を用いた含浸法(特許文献1)による金ナノ粒子担持体の調製法が報告されている。しかしながら、酢酸金は水への溶解性が低く、当該手法においては塩化物イオンフリーの含浸液の調製のために複数工程が必要となる。
However, it is difficult to produce a gold fine particle carrier by an impregnation method. This is because chloride ions increase the particle size of gold when prepared by an impregnation method using chloroauric acid (Non-patent Document 1). Conventionally, preparation of a gold fine particle catalyst has been performed by a coprecipitation method or a precipitation method. In recent years, a method for preparing a gold nanoparticle carrier by an impregnation method using gold acetate (Patent Document 1) has been reported. However, gold acetate has low solubility in water, and this method requires a plurality of steps for preparing a chloride ion-free impregnation solution.
本発明は、金等の金属微粒子を担体上に担持させた金属微粒子担持体を、簡便な工程で低コストで製造することを可能にする新規な手段を提供することを目的とする。
An object of the present invention is to provide a novel means that makes it possible to produce a metal fine particle carrier in which metal fine particles such as gold are supported on a carrier by a simple process at a low cost.
本願発明者らは、鋭意研究の結果、後周期遷移金属にアミノ酸分子又はアミノ酸類似化合物が配位した錯体は塩化金酸から短工程で調製可能であること、この後周期遷移金属/アミノ酸錯体又は後周期遷移金属/アミノ酸類似化合物錯体を含浸法における金属前駆体として用いることにより、金を用いた場合であってもナノサイズの粒子を調製できること、後周期遷移金属/アミノ酸錯体及び後周期遷移金属/アミノ酸類似化合物錯体は水への溶解性が良好であり、含浸工程において用いる水溶媒の量はごく少量で済むために廃液量も低減でき、低コストで金属微粒子担持体を調製可能となることを見出し、本願発明を完成した。
As a result of intensive studies, the present inventors have found that a complex in which an amino acid molecule or an amino acid analog is coordinated to a late transition metal can be prepared from chloroauric acid in a short process, and that this late transition metal / amino acid complex or By using the late transition metal / amino acid analog compound complex as a metal precursor in the impregnation method, nano-sized particles can be prepared even when gold is used, the late transition metal / amino acid complex, and the late transition metal. / The amino acid analog compound complex has good solubility in water, and since the amount of the aqueous solvent used in the impregnation step is very small, the amount of waste liquid can be reduced, and the metal fine particle support can be prepared at low cost. The present invention was completed.
すなわち、本発明は、後周期遷移金属/アミノ酸錯体及び後周期遷移金属/アミノ酸類似化合物錯体からなる群より選択される少なくとも1種の錯体の溶液と担体を混和して、前記少なくとも1種の錯体を担体に含浸させる工程、及び錯体含浸後の担体を焼成する工程を含む、後周期遷移金属微粒子担持体の製造方法を提供する。また、本発明は、後周期遷移金属にアミノ酸(ただしグリシン、ヒスチジン及びトリプトファンを除く)又はアミノ酸類似化合物が配位してなる金属錯体を提供する。
That is, the present invention comprises mixing at least one complex solution selected from the group consisting of late-period transition metal / amino acid complex and late-period transition metal / amino acid analog compound complex with a carrier, and said at least one complex. A method for producing a late transition metal fine particle carrier comprising a step of impregnating a carrier with a carrier and a step of firing the carrier after impregnation with a complex is provided. The present invention also provides a metal complex in which an amino acid (excluding glycine, histidine, and tryptophan) or an amino acid analog is coordinated to a late transition metal.
本発明により、金属前駆体として後周期遷移金属にアミノ酸又はアミノ酸類似化合物が配位した錯体を利用した含浸法による後周期遷移金属微粒子担持体の製造方法が初めて提供される。後周期遷移金属/アミノ酸錯体及び後周期遷移金属/アミノ酸類似化合物錯体は水への溶解性が良好であり、含浸液の調製は水等の溶媒に錯体を溶解するのみで極めて簡便である。また水への溶解度の高さゆえに溶媒の使用量も少なく抑えることができ、含浸液のボリュームダウンが可能であるとともに廃液量の低減も可能であり、低コストでの大量生産に適している。上記の錯体自体も調製は容易であり、安価な原料で錯体を製造できる。含浸液は塩化物イオンフリーであるため、本発明による含浸法は金ナノ粒子担持体の調製にも適用可能である。さらに、本発明の方法によれば、通常は使用困難な酸性担体でも使用可能であるので、担体の種類に左右されることなく、様々な担体を用いて極小サイズの金属微粒子担持体を調製することができる。
The present invention provides for the first time a method for producing a late transition metal fine particle support by an impregnation method using a complex in which an amino acid or an amino acid analog is coordinated to a late transition metal as a metal precursor. The late transition metal / amino acid complex and the late transition metal / amino acid analog compound complex have good solubility in water, and the preparation of the impregnation solution is very simple only by dissolving the complex in a solvent such as water. In addition, since the solubility in water is high, the amount of the solvent used can be reduced, the volume of the impregnating liquid can be reduced, and the amount of the waste liquid can be reduced, which is suitable for mass production at a low cost. The above complex itself is easy to prepare, and the complex can be produced from inexpensive raw materials. Since the impregnation solution is free of chloride ions, the impregnation method according to the present invention can also be applied to the preparation of a gold nanoparticle carrier. Furthermore, according to the method of the present invention, even an acidic carrier that is usually difficult to use can be used. Therefore, a metal particle carrier having a very small size is prepared using various carriers, regardless of the type of the carrier. be able to.
本発明の製造方法では、担体上に含浸担持させる金属前駆体として、後周期遷移金属にアミノ酸が配位した後周期遷移金属/アミノ酸錯体、及び後周期遷移金属にアミノ酸類似化合物が配位した後周期遷移金属/アミノ酸類似化合物錯体からなる群より選択される少なくとも1種を用いることを特徴とする。以下、本明細書において、アミノ酸及びアミノ酸類似化合物を総称して「アミノ酸系化合物」と呼ぶことがある。
In the production method of the present invention, as a metal precursor to be impregnated and supported on a support, a late transition metal / amino acid complex in which an amino acid is coordinated to a late transition metal and an amino acid analog compound to a late transition metal are coordinated It is characterized by using at least one selected from the group consisting of a periodic transition metal / amino acid analog compound complex. Hereinafter, in the present specification, amino acids and amino acid analogs may be collectively referred to as “amino acid compounds”.
本発明において、後周期遷移金属には、金、銀、白金、パラジウム、ルテニウム、ロジウム、オスミウム、イリジウム、鉄、コバルト、ニッケル、銅、亜鉛及び鉛が包含され、これらの金属のうちの少なくとも1種を使用可能である。中でも好ましく使用し得る金属として、金、銀、白金、及びパラジウムからなる群より選択される少なくとも1種、特に金を挙げることができるが、これらに限定されない。
In the present invention, the late transition metals include gold, silver, platinum, palladium, ruthenium, rhodium, osmium, iridium, iron, cobalt, nickel, copper, zinc and lead, and at least one of these metals. Species can be used. Among them, examples of metals that can be preferably used include at least one selected from the group consisting of gold, silver, platinum, and palladium, in particular, gold, but are not limited thereto.
金属に配位させるアミノ酸の種類は特に限定されない。本発明において、「アミノ酸」とは、分子内にアミノ基とカルボキシ基とを持つ化合物をいい、一般的なアミノ酸の定義の通り、アミノ基の水素が分子内の他の部分と置換して二級アミンとなった環状化合物であるイミノ酸も包含する。本発明で使用できるアミノ酸の代表的な例としては、天然のタンパク質を構成する20種のα-アミノ酸が挙げられるが、これらに限定されず、β-、γ-及びδ-アミノ酸も包含される。また、アミノ酸はD体でもL体でもよく、両者の混合物でもよい。アミノ酸の具体例を挙げると、アルギニン、ヒスチジン、リジン、アスパラギン酸、グルタミン酸、アラニン、グリシン、ロイシン、バリン、イソロイシン、セリン、スレオニン、フェニルアラニン、トリプトファン、チロシン、シスチン又はシステイン、グルタミン、アスパラギン、プロリン、メチオニン、β-アラニン、γ-アミノ酪酸(4-アミノ酪酸)、カルニチン、γ-アミノレブリン酸、γ-アミノ吉草酸、δ-アミノ吉草酸(5-アミノ吉草酸)、ε-アミノカプロン酸(6-アミノカプロン酸)などが挙げられる。なお、金とアミノ酸との間の錯体として、グリシン、ヒスチジン、及びトリプトファンとの錯体が公知である(Pharmaceutical Chemistry Journal, 1999, vol.33, No.9, p.11-13)。
The type of amino acid coordinated to the metal is not particularly limited. In the present invention, an “amino acid” refers to a compound having an amino group and a carboxy group in the molecule. As defined in general amino acids, the amino group hydrogen is substituted for other parts in the molecule. Also included are imino acids, which are cyclic compounds that have been converted to secondary amines. Representative examples of amino acids that can be used in the present invention include, but are not limited to, 20 α-amino acids constituting natural proteins, and β-, γ-, and δ-amino acids are also included. . The amino acid may be D-form or L-form, or a mixture of both. Specific examples of amino acids include arginine, histidine, lysine, aspartic acid, glutamic acid, alanine, glycine, leucine, valine, isoleucine, serine, threonine, phenylalanine, tryptophan, tyrosine, cystine or cysteine, glutamine, asparagine, proline, methionine. , Β-alanine, γ-aminobutyric acid (4-aminobutyric acid), carnitine, γ-aminolevulinic acid, γ-aminovaleric acid, δ-aminovaleric acid (5-aminovaleric acid), ε-aminocaproic acid (6-aminocapron) Acid). As complexes between gold and amino acids, complexes of glycine, histidine, and tryptophan are known (Pharmaceutical Chemistry Journal, 1999, vol.33, No.9, p.11-13).
アミノ酸類似化合物も、上記定義の通りのアミノ酸に類似した構造を有する限り特に限定されない。アミノ酸類似化合物の例としては、
アミノ酸分子の少なくとも1個(例えば全部、又は1個若しくは2個、又は1個)のアミノ基がスルフヒドリル基に置き換わった化合物;
アミノ酸分子の少なくとも1個(例えば全部、又は1個若しくは2個、又は1個)のアミノ基に少なくとも1個のアルキル基が結合した化合物(アルキル基の炭素数は例えば1~5個、1~4個、1~3個、1個若しくは2個、又は1個);
アミノ酸分子の主鎖及び側鎖を構成する炭素原子の少なくとも1個(例えば1~5個、又は1~3個、又は1個若しくは2個、又は1個)が窒素原子、酸素原子及び硫黄原子から選択される少なくとも1つに置き換わった化合物;並びに
アミノ酸分子の主鎖及び側鎖を構成する炭素原子の少なくとも1個(例えば1~5個、1~4個、1~3個、1個若しくは2個、又は1個)に、アルキル基、水酸基及びハロゲン原子からなる群より選択される少なくとも1つが結合した化合物(アルキル基の炭素数は例えば1~5個、1~4個、1~3個、1個若しくは2個、又は1個)
等を挙げることができる。 An amino acid analog compound is not particularly limited as long as it has a structure similar to an amino acid as defined above. Examples of amino acid analogs include
A compound in which at least one (for example, all or one or two, or one) amino group of an amino acid molecule is replaced with a sulfhydryl group;
A compound in which at least one alkyl group is bonded to at least one (for example, all, one, two, or one) amino group of an amino acid molecule (the carbon number of the alkyl group is, for example, 1 to 5, 1 to 4, 1 to 3, 1 or 2, or 1);
At least one (for example, 1 to 5, or 1 to 3, or 1 or 2, or 1) carbon atoms constituting the main chain and side chain of the amino acid molecule are a nitrogen atom, an oxygen atom, and a sulfur atom. A compound substituted with at least one selected from: and at least one of carbon atoms constituting the main chain and side chain of the amino acid molecule (eg, 1 to 5, 1 to 4, 1 to 3, 1 or A compound in which at least one selected from the group consisting of an alkyl group, a hydroxyl group and a halogen atom is bonded to two or one (the number of carbons in the alkyl group is, for example, 1 to 5, 1 to 4, 1 to 3) Piece, one piece, two pieces, or one piece)
Etc.
アミノ酸分子の少なくとも1個(例えば全部、又は1個若しくは2個、又は1個)のアミノ基がスルフヒドリル基に置き換わった化合物;
アミノ酸分子の少なくとも1個(例えば全部、又は1個若しくは2個、又は1個)のアミノ基に少なくとも1個のアルキル基が結合した化合物(アルキル基の炭素数は例えば1~5個、1~4個、1~3個、1個若しくは2個、又は1個);
アミノ酸分子の主鎖及び側鎖を構成する炭素原子の少なくとも1個(例えば1~5個、又は1~3個、又は1個若しくは2個、又は1個)が窒素原子、酸素原子及び硫黄原子から選択される少なくとも1つに置き換わった化合物;並びに
アミノ酸分子の主鎖及び側鎖を構成する炭素原子の少なくとも1個(例えば1~5個、1~4個、1~3個、1個若しくは2個、又は1個)に、アルキル基、水酸基及びハロゲン原子からなる群より選択される少なくとも1つが結合した化合物(アルキル基の炭素数は例えば1~5個、1~4個、1~3個、1個若しくは2個、又は1個)
等を挙げることができる。 An amino acid analog compound is not particularly limited as long as it has a structure similar to an amino acid as defined above. Examples of amino acid analogs include
A compound in which at least one (for example, all or one or two, or one) amino group of an amino acid molecule is replaced with a sulfhydryl group;
A compound in which at least one alkyl group is bonded to at least one (for example, all, one, two, or one) amino group of an amino acid molecule (the carbon number of the alkyl group is, for example, 1 to 5, 1 to 4, 1 to 3, 1 or 2, or 1);
At least one (for example, 1 to 5, or 1 to 3, or 1 or 2, or 1) carbon atoms constituting the main chain and side chain of the amino acid molecule are a nitrogen atom, an oxygen atom, and a sulfur atom. A compound substituted with at least one selected from: and at least one of carbon atoms constituting the main chain and side chain of the amino acid molecule (eg, 1 to 5, 1 to 4, 1 to 3, 1 or A compound in which at least one selected from the group consisting of an alkyl group, a hydroxyl group and a halogen atom is bonded to two or one (the number of carbons in the alkyl group is, for example, 1 to 5, 1 to 4, 1 to 3) Piece, one piece, two pieces, or one piece)
Etc.
アミノ酸類似化合物の具体例としては、チオリンゴ酸(アスパラギン酸の-NH2基が-SH基に置き換わったアスパラギン酸類似化合物)、p-クロロフェニルアラニン(フェニル基のパラ位が塩素原子で置換されたフェニルアラニン類似化合物)、β-クロロアラニン(β炭素が塩素原子で置換されたアラニン類似化合物)、ヒドロキシプロリン(ヒドロキシル化されたプロリン、コラーゲン構成成分)、ヒドロキシリジン(ヒドロキシル化されたリジン、コラーゲン構成成分)、サルコシン(Nメチルグリシン、グリシンのアミノ基に1個のメチル基が結合したグリシン類似化合物)などを挙げることができるが、これらに限定されない。
Specific examples of amino acid analogs include thiomalic acid (aspartic acid analog in which the —NH 2 group of aspartic acid is replaced with —SH group), p-chlorophenylalanine (phenylalanine in which the para position of the phenyl group is substituted with a chlorine atom) Similar compounds), β-chloroalanine (Alanine analogs in which the β carbon is replaced by chlorine atoms), hydroxyproline (hydroxylated proline, collagen component), hydroxylysine (hydroxylated lysine, collagen component) Sarcosine (N-methylglycine, a glycine-like compound in which one methyl group is bonded to the amino group of glycine), and the like, but is not limited thereto.
担体の種類は特に限定されず、後周期遷移金属をナノサイズ以下の粒子状でその表面に担持することができる担体であればいかなるものであってもよい。本発明の方法によれば、通常の含浸法では使用困難な酸性担体でも使用可能である。担体の具体例を挙げると、ケイ素材料(シリカ、シリカ-アルミナ、アルミノケイ酸塩等)、炭素材料(活性炭、及び各種の多孔性炭素材料等)、金属酸化物(酸化鉄、酸化アルミニウム、酸化チタン、酸化コバルト、酸化ジルコニウム、酸化セリウム、酸化マンガン、酸化亜鉛、酸化ニッケル、酸化マグネシウム、酸化タングステン等)、粘土(ベントナイト、活性白土、珪藻土、モンモリロナイト等)、合成又は天然ポリマー(各種の合成樹脂、ポリビニルピロリドン、キトサン、微小繊維状セルロース、タンニン、寒天、ゼラチン等)、炭酸塩(炭酸マグネシウム、炭酸カルシウム、炭酸バリウム等)、多孔性配位高分子(Porous Coordination Polymer; PCP、金属イオンとそれらを架橋する有機配位子とで構成される結晶性の高分子構造体であり、金属有機構造体(Metal-Organic Framework; MOF)とも呼ばれる)、窒化ホウ素等を挙げることができるが、これらに限定されない。
The type of the carrier is not particularly limited, and any carrier can be used as long as it can carry the late transition metal in the form of nano-sized particles or less on the surface thereof. According to the method of the present invention, it is possible to use an acidic carrier which is difficult to use by a normal impregnation method. Specific examples of the carrier include silicon materials (silica, silica-alumina, aluminosilicate, etc.), carbon materials (activated carbon, various porous carbon materials, etc.), metal oxides (iron oxide, aluminum oxide, titanium oxide). , Cobalt oxide, zirconium oxide, cerium oxide, manganese oxide, zinc oxide, nickel oxide, magnesium oxide, tungsten oxide, etc.), clay (bentonite, activated clay, diatomaceous earth, montmorillonite, etc.), synthetic or natural polymers (various synthetic resins, Polyvinylpyrrolidone, chitosan, microfibrous cellulose, tannin, agar, gelatin, etc., carbonate (magnesium carbonate, calcium carbonate, barium carbonate, etc.), porous coordination polymer (Porous Coordination Polymer; PCP, metal ions and those A crystalline polymer structure composed of a bridging organic ligand Ri, metal organic structures; also referred to as (Metal-Organic Framework MOF)), there may be mentioned boron nitride, and the like.
担体の形状も特に限定されず、いかなる形状・形態であってもよい。例えば、粉末状、顆粒状、ペレット状、ハニカム状等、様々な形状のものを使用可能である。担体の比表面積は特に限定されないが、通常、比表面積が大きい多孔質の担体(例えば、概ね30m2/g程度以上、特に100m2/g程度以上)が好ましく使用される。比表面積の上限も特に限定されないが、通常3000m2/g程度以下である。
The shape of the carrier is not particularly limited, and may be any shape / form. For example, various shapes such as powder, granules, pellets, and honeycombs can be used. The specific surface area of the carrier is not particularly limited, but usually a porous carrier having a large specific surface area (for example, about 30 m 2 / g or more, particularly about 100 m 2 / g or more) is preferably used. The upper limit of the specific surface area is not particularly limited, but is usually about 3000 m 2 / g or less.
後周期遷移金属/アミノ酸系化合物錯体の調製方法の具体例は、下記実施例に記載される通りである。簡単に記載すると、アミノ酸系化合物を塩基性のアルコール水溶液溶媒中に溶解し、これに後周期遷移金属の可溶性化合物のアルコール水溶液を添加し、さらにアルコールを加えて錯体を析出させ、これを回収し適宜アルコールで再沈殿後に洗浄することにより、後周期遷移金属/アミノ酸系化合物錯体を得ることができる。アルコールとしてはエタノール等の低級アルコールを用いればよい。後周期遷移金属の可溶性化合物の具体例として、金の場合は塩化金酸;白金の場合は塩化白金酸及び硝酸白金;銀の場合は硝酸銀;パラジウムの場合は塩化パラジウム及び硝酸パラジウム、等を挙げることができる。
Specific examples of the method for preparing the late transition metal / amino acid compound complex are as described in the following examples. Briefly, an amino acid compound is dissolved in a basic alcohol aqueous solvent, an alcohol aqueous solution of a late transition metal soluble compound is added thereto, and an alcohol is further added to precipitate a complex, which is recovered. By washing after reprecipitation with an appropriate alcohol, a late transition metal / amino acid compound complex can be obtained. A lower alcohol such as ethanol may be used as the alcohol. Specific examples of late transition metal soluble compounds include chloroauric acid in the case of gold; chloroplatinic acid and platinum nitrate in the case of platinum; silver nitrate in the case of silver; palladium chloride and palladium nitrate in the case of palladium. be able to.
後周期遷移金属/アミノ酸系化合物錯体の担体への含浸担持は、錯体を水に溶解し、これに担体を添加して撹拌混和した後に焼成することにより行なえばよい。配位したアミノ酸系化合物が異なる錯体を混合して担体に含浸させてもよい。錯体を溶解させる時の水をできるだけ少量とし、担体と錯体水溶液を撹拌混和して担体に錯体を含浸させた後、乾燥させずにすぐに焼成処理に付すことにより、担体上の金属微粒子のサイズを10nm程度以下に小さくすることができるということが、金を用いた実験により確認されている。乾燥工程を経て焼成処理を行なった場合には、平均粒径がやや大きめ(10nm~30nm程度)の金属粒子を調製することができる。担体との撹拌混和時間は特に限定されず、数分~数十分程度で十分である。焼成温度は100℃~600℃程度、例えば150℃~400℃程度でよい。焼成時間は数分~十数時間程度、例えば20分~10時間程度でよい。焼成は、空気等の含酸素雰囲気中で行なってもよいし、還元性ガス雰囲気中又は不活性ガス雰囲気中で行なってもよい。焼成処理により錯体中に含まれていたアミノ酸系化合物は消失するので、触媒活性等の性能を低下させる不要成分が担体上に残存する懸念はない。
The impregnation support on the carrier of the late transition metal / amino acid compound complex may be carried out by dissolving the complex in water, adding the carrier to this, stirring and mixing, and firing. Complexes with different coordinated amino acid compounds may be mixed and impregnated into the carrier. The size of the metal fine particles on the carrier is reduced by reducing the amount of water used to dissolve the complex as much as possible, stirring and mixing the carrier and the complex aqueous solution, impregnating the carrier with the complex, and immediately subjecting it to firing without drying. It has been confirmed by experiments using gold that can be reduced to about 10 nm or less. When the baking treatment is performed through the drying process, metal particles having a slightly larger average particle diameter (about 10 nm to 30 nm) can be prepared. The stirring and mixing time with the carrier is not particularly limited, and a few minutes to several tens of minutes is sufficient. The firing temperature may be about 100 ° C. to 600 ° C., for example, about 150 ° C. to 400 ° C. The firing time may be about several minutes to over a dozen hours, for example, about 20 minutes to 10 hours. Firing may be performed in an oxygen-containing atmosphere such as air, or may be performed in a reducing gas atmosphere or an inert gas atmosphere. Since the amino acid compound contained in the complex disappears due to the calcination treatment, there is no concern that unnecessary components that lower the performance such as catalytic activity remain on the support.
本発明によれば、平均粒径50nm程度以下の後周期遷移金属微粒子が担体上に担持された金属微粒子担持体を得ることができる。ここで、担体上に担持された金属微粒子の「粒径」「粒子サイズ」との文言は、略半球状で担体上に固定化されている金属微粒子の直径をいう。金属微粒子のサイズは、上記した各条件の範囲内で製造条件を調節することにより、サイズ調整が可能である。例えば、平均粒径を10nm程度以下の極小サイズにしたい場合、多孔質でも比較的比表面積が小さめのもの(300~400m2/g程度以下)を担体として用いる、アミノ酸との錯体を担体に含浸させた後乾燥させずに焼成する、等の条件で含浸担持を行なえばよい。水への溶解度が特に高い後周期遷移金属/アミノ酸系化合物錯体を用いることによっても、担体上に担持される金属微粒子のサイズを小さくすることができる。本発明の方法により得られる担体上の金属微粒子のサイズの下限値は特に限定されないが、通常は平均粒径0.5 nm以上、例えば平均粒径1 nm程度以上である。
According to the present invention, it is possible to obtain a metal fine particle carrier in which late-period transition metal fine particles having an average particle size of about 50 nm or less are supported on a carrier. Here, the terms “particle size” and “particle size” of the metal fine particles supported on the carrier refer to the diameter of the metal fine particles which are substantially hemispherical and fixed on the carrier. The size of the metal fine particles can be adjusted by adjusting the production conditions within the range of the above-described conditions. For example, if you want to make the average particle size as small as 10 nm or less, use a porous material with a relatively small specific surface area (300 to 400 m 2 / g or less) as a carrier, impregnating the carrier with a complex with an amino acid Then, the impregnation support may be carried out under conditions such as firing without drying. The size of the metal fine particles supported on the carrier can also be reduced by using a late transition metal / amino acid compound complex having a particularly high solubility in water. The lower limit of the size of the metal fine particles on the support obtained by the method of the present invention is not particularly limited, but is usually an average particle size of 0.5 nm or more, for example, an average particle size of about 1 nm or more.
本発明の製造方法により得られる後周期遷移金属微粒子担持体は、通常、金属の担持量が0.1~30wt%程度である。
The late transition metal fine particle carrier obtained by the production method of the present invention usually has a metal loading of about 0.1 to 30 wt%.
本発明の方法で製造される後周期遷移金属微粒子担持体は、従来より知られている各種貴金属触媒と同様に触媒として使用可能である。例えば、公知の金ナノ粒子触媒は、環境中の有害成分の分解、燃料電池関連反応(アノード反応など)、プロピレン、スチレンの気相エポキシ化などの化学プロセス反応等の様々な反応を触媒することが知られているが、本発明の方法で金/アミノ酸系化合物錯体を用いて製造される金微粒子担持体も、公知の金ナノ粒子触媒と同様に様々な反応の触媒として利用可能である。
The late transition metal fine particle carrier produced by the method of the present invention can be used as a catalyst in the same manner as various types of noble metal catalysts known in the art. For example, known gold nanoparticle catalysts catalyze various reactions such as decomposition of harmful components in the environment, fuel cell-related reactions (anodic reactions, etc.), chemical process reactions such as propylene, styrene gas phase epoxidation, etc. However, the gold fine particle carrier produced by using the gold / amino acid compound complex by the method of the present invention can also be used as a catalyst for various reactions in the same manner as the known gold nanoparticle catalyst.
また、触媒以外にも、吸着剤、力学材料、光学材料、電磁気材料等への応用も可能である。例えば、金の微粒子は硫黄化合物を吸着する作用を有することが知られており(特許第5170591号)、本発明の方法で製造される金微粒子担持体も、硫黄化合物の吸着剤として用いることができる。例えば、ジメチルトリスルフィド、ジメチルジスルフィド等のポリスルフィドは、清酒の劣化臭である老香の主要構成成分であるが(日本醸造協会誌, 101, 125-131, 2006)、後周期遷移金属微粒子担持体は、そのようなポリスルフィドの吸着除去剤として、清酒における老香の低減にも利用可能である。また、本発明の方法で製造される後周期遷移金属微粒子担持体は、水系の液体からの硫黄化合物の吸着除去だけではなく、特許第5170591号記載の発明と同様に、ガソリン等の液体燃料や有機溶媒などの親油性の液体から硫黄化合物を吸着除去する吸着剤としても利用可能である。
Besides the catalyst, application to adsorbents, mechanical materials, optical materials, electromagnetic materials, etc. is also possible. For example, gold fine particles are known to have an action of adsorbing sulfur compounds (Japanese Patent No. 5170591), and gold fine particle carriers produced by the method of the present invention can also be used as sulfur compound adsorbents. it can. For example, polysulfides such as dimethyl trisulfide and dimethyl disulfide are the main constituents of Oika, which is a deteriorated odor of sake (Japan Brewing Association, 101, 125-131, 2006). Can be used as a polysulfide adsorption / removal agent for the reduction of scent in sake. Further, the late transition metal fine particle carrier produced by the method of the present invention is not only used for adsorption removal of sulfur compounds from aqueous liquids, but also for liquid fuels such as gasoline, as in the invention described in Japanese Patent No. 5170591. It can also be used as an adsorbent for adsorbing and removing sulfur compounds from lipophilic liquids such as organic solvents.
以下、本発明を実施例に基づきより具体的に説明する。もっとも、本発明は下記実施例に限定されるものではない。
Hereinafter, the present invention will be described more specifically based on examples. However, the present invention is not limited to the following examples.
1.金/アミノ酸錯体を用いた含浸法によるAu担持シリカ(Au/SiO2)の調製
まず、金/グリシン錯体を使用し、含浸法による調製の条件を検討した。 1. Preparation of Au-supported silica (Au / SiO 2 ) by an impregnation method using a gold / amino acid complex First, the preparation conditions by the impregnation method were examined using a gold / glycine complex.
まず、金/グリシン錯体を使用し、含浸法による調製の条件を検討した。 1. Preparation of Au-supported silica (Au / SiO 2 ) by an impregnation method using a gold / amino acid complex First, the preparation conditions by the impregnation method were examined using a gold / glycine complex.
(1) 金/グリシン錯体の調製
ビーカー内で水酸化ナトリウム2.5 mmol、グリシン2.5 mmolを水2 mLに溶かし、エタノール3mLを加えた。フラスコで塩化金酸四水和物0.32 mmolを水1 mLに溶かし、エタノール4mLを加えた。フラスコの塩化金酸溶液をビーカーに加え、エタノール6 mLで洗い出した後、冷凍庫に一晩放置した。透明の上澄みを取り除き、少量の水で沈殿物を溶かし、エタノールで再沈殿させ、遠心分離器で上澄みを捨てた。エタノールで遠心洗浄を2回行った。金/グリシン錯体Au(gly)(OH)2をろ取し、真空乾燥させた。 (1) Preparation of gold / glycine complex 2.5 mmol of sodium hydroxide and 2.5 mmol of glycine were dissolved in 2 mL of water in a beaker, and 3 mL of ethanol was added. In a flask, 0.32 mmol of chloroauric acid tetrahydrate was dissolved in 1 mL of water, and 4 mL of ethanol was added. The chloroauric acid solution in the flask was added to a beaker, washed with 6 mL of ethanol, and then left overnight in a freezer. The clear supernatant was removed, the precipitate was dissolved with a small amount of water, reprecipitated with ethanol, and the supernatant was discarded with a centrifuge. Centrifugal washing was performed twice with ethanol. The gold / glycine complex Au (gly) (OH) 2 was collected by filtration and dried in vacuo.
ビーカー内で水酸化ナトリウム2.5 mmol、グリシン2.5 mmolを水2 mLに溶かし、エタノール3mLを加えた。フラスコで塩化金酸四水和物0.32 mmolを水1 mLに溶かし、エタノール4mLを加えた。フラスコの塩化金酸溶液をビーカーに加え、エタノール6 mLで洗い出した後、冷凍庫に一晩放置した。透明の上澄みを取り除き、少量の水で沈殿物を溶かし、エタノールで再沈殿させ、遠心分離器で上澄みを捨てた。エタノールで遠心洗浄を2回行った。金/グリシン錯体Au(gly)(OH)2をろ取し、真空乾燥させた。 (1) Preparation of gold / glycine complex 2.5 mmol of sodium hydroxide and 2.5 mmol of glycine were dissolved in 2 mL of water in a beaker, and 3 mL of ethanol was added. In a flask, 0.32 mmol of chloroauric acid tetrahydrate was dissolved in 1 mL of water, and 4 mL of ethanol was added. The chloroauric acid solution in the flask was added to a beaker, washed with 6 mL of ethanol, and then left overnight in a freezer. The clear supernatant was removed, the precipitate was dissolved with a small amount of water, reprecipitated with ethanol, and the supernatant was discarded with a centrifuge. Centrifugal washing was performed twice with ethanol. The gold / glycine complex Au (gly) (OH) 2 was collected by filtration and dried in vacuo.
(2) 担体への金の含浸担持
金/グリシン錯体15 mgを乳鉢に入れ、水を0.5mL加えて溶かし、そこに990 mgのSiO2(富士シリシア化学、CARiACT Q-15、比表面積200m2/g)を加えて30分間撹拌混和した。その後、乾燥させずにすぐ空気焼成(300℃、4時間)を行ない、金粒子をSiO2上に担持させた。 (2) Impregnation of gold on the support 15 mg of gold / glycine complex is placed in a mortar and 0.5 mL of water is added and dissolved, and then 990 mg of SiO 2 (Fuji Silysia Chemical, CARiACT Q-15, specific surface area 200 m 2 / g) was added and mixed with stirring for 30 minutes. Thereafter, air baking (300 ° C., 4 hours) was immediately performed without drying, and gold particles were supported on SiO 2 .
金/グリシン錯体15 mgを乳鉢に入れ、水を0.5mL加えて溶かし、そこに990 mgのSiO2(富士シリシア化学、CARiACT Q-15、比表面積200m2/g)を加えて30分間撹拌混和した。その後、乾燥させずにすぐ空気焼成(300℃、4時間)を行ない、金粒子をSiO2上に担持させた。 (2) Impregnation of gold on the support 15 mg of gold / glycine complex is placed in a mortar and 0.5 mL of water is added and dissolved, and then 990 mg of SiO 2 (Fuji Silysia Chemical, CARiACT Q-15, specific surface area 200 m 2 / g) was added and mixed with stirring for 30 minutes. Thereafter, air baking (300 ° C., 4 hours) was immediately performed without drying, and gold particles were supported on SiO 2 .
(3) 含浸担持の条件検討
上記(2)の条件を基準とし、条件を種々に変更して含浸担持の条件検討を行なった。検討した条件及びその結果(担持された金粒子の平均粒径、XRDにより測定)を併せて下記表1に示す。 (3) Examination of impregnation support conditions Based on the above condition (2), the impregnation support conditions were examined by changing the conditions in various ways. The examined conditions and the results (average particle diameter of supported gold particles, measured by XRD) are shown together in Table 1 below.
上記(2)の条件を基準とし、条件を種々に変更して含浸担持の条件検討を行なった。検討した条件及びその結果(担持された金粒子の平均粒径、XRDにより測定)を併せて下記表1に示す。 (3) Examination of impregnation support conditions Based on the above condition (2), the impregnation support conditions were examined by changing the conditions in various ways. The examined conditions and the results (average particle diameter of supported gold particles, measured by XRD) are shown together in Table 1 below.
(4) 析出還元(DR)法によるAu/SiO2-(DR)の調製
参考例として、析出還元(DR)法によるAu/SiO2の調製も行なった。下記の手順により、[Au(en)2Cl3]をNaBH4で還元させてAu担持シリカ(Au/SiO2-(DR))を調製した。 (4) precipitation reduction (DR) method by Au / SiO 2 - Preparation Example of (DR), was also performed Preparation of Au / SiO 2 by precipitation reduction (DR) method. According to the following procedure, [Au (en) 2 Cl 3 ] was reduced with NaBH 4 to prepare Au-supported silica (Au / SiO 2- (DR)).
参考例として、析出還元(DR)法によるAu/SiO2の調製も行なった。下記の手順により、[Au(en)2Cl3]をNaBH4で還元させてAu担持シリカ(Au/SiO2-(DR))を調製した。 (4) precipitation reduction (DR) method by Au / SiO 2 - Preparation Example of (DR), was also performed Preparation of Au / SiO 2 by precipitation reduction (DR) method. According to the following procedure, [Au (en) 2 Cl 3 ] was reduced with NaBH 4 to prepare Au-supported silica (Au / SiO 2- (DR)).
ナスフラスコに水250mL、シリカゲル990 mg、[Au(en)2Cl3]を11 mg加えた。0℃で30分撹拌した後、0.01 MのNaBH4 3.8 mLを10分かけてゆっくり滴下した。1時間撹拌した後、ろ取し、水で洗い、真空乾燥させた。得られたAu担持シリカAu/SiO2-(DR)の平均粒径(XDRにより測定)は11.0 nmであった。
To the eggplant flask, 250 mL of water, 990 mg of silica gel, and 11 mg of [Au (en) 2 Cl 3 ] were added. After stirring at 0 ° C. for 30 minutes, 0.01 M NaBH 4 3.8 mL was slowly added dropwise over 10 minutes. After stirring for 1 hour, it was collected by filtration, washed with water, and dried in vacuo. The average particle size (measured by XDR) of the obtained Au-supported silica Au / SiO 2- (DR) was 11.0 nm.
<結果>
金/グリシン錯体含浸法では、条件[1]~[3]、[6]~[8]、[10]で5nm程度以下の小さいサイズの金粒子を調製することができた。条件[4]及び[5](乾燥工程あり)、条件[9](シリカ担体の比表面積大)、並びにDR法では、10nm程度以上のやや大きめの金粒子が調製された。 <Result>
In the gold / glycine complex impregnation method, gold particles having a small size of about 5 nm or less could be prepared under the conditions [1] to [3], [6] to [8], and [10]. In the conditions [4] and [5] (with a drying step), the condition [9] (large specific surface area of the silica support), and the DR method, slightly larger gold particles of about 10 nm or more were prepared.
金/グリシン錯体含浸法では、条件[1]~[3]、[6]~[8]、[10]で5nm程度以下の小さいサイズの金粒子を調製することができた。条件[4]及び[5](乾燥工程あり)、条件[9](シリカ担体の比表面積大)、並びにDR法では、10nm程度以上のやや大きめの金粒子が調製された。 <Result>
In the gold / glycine complex impregnation method, gold particles having a small size of about 5 nm or less could be prepared under the conditions [1] to [3], [6] to [8], and [10]. In the conditions [4] and [5] (with a drying step), the condition [9] (large specific surface area of the silica support), and the DR method, slightly larger gold particles of about 10 nm or more were prepared.
2.アミノ酸系化合物の検討
アミノ酸として、グリシンに加え、β-アラニン、4-アミノ酪酸、リジン、アスパラギン、D,L-アラニン、5-アミノ吉草酸、6-アミノカプロン酸、メチオニン、グルタミン酸、ヒスチジン、トリプトファンを用いた。また、アミノ酸類似化合物として、チオリンゴ酸を用いた。ビーカー内で水酸化ナトリウム2.5 mmol、アミノ酸系化合物2.5 mmolを水2 mLに溶かし、エタノール3mLを加えた。フラスコで塩化金酸四水和物0.32 mmolを水1 mLに溶かし、エタノール4mLを加えた。フラスコの塩化金酸溶液をビーカーに加え、エタノール6 mLで洗い出した。冷凍庫に一晩放置した。透明の上澄みを取り除き、少量の水で沈殿物を溶かし、エタノールで再沈殿させ、遠心分離器で上澄みを捨てた。エタノールで遠心洗浄を2回行った。錯体をろ取し、真空乾燥させた。 2. Amino acid compounds In addition to glycine, amino acids include β-alanine, 4-aminobutyric acid, lysine, asparagine, D, L-alanine, 5-aminovaleric acid, 6-aminocaproic acid, methionine, glutamic acid, histidine, and tryptophan. Using. Moreover, thiomalic acid was used as an amino acid analog. In a beaker, 2.5 mmol of sodium hydroxide and 2.5 mmol of an amino acid compound were dissolved in 2 mL of water, and 3 mL of ethanol was added. In a flask, 0.32 mmol of chloroauric acid tetrahydrate was dissolved in 1 mL of water, and 4 mL of ethanol was added. The chloroauric acid solution in the flask was added to a beaker and washed with 6 mL of ethanol. Left in the freezer overnight. The clear supernatant was removed, the precipitate was dissolved with a small amount of water, reprecipitated with ethanol, and the supernatant was discarded with a centrifuge. Centrifugal washing was performed twice with ethanol. The complex was collected by filtration and dried in vacuo.
アミノ酸として、グリシンに加え、β-アラニン、4-アミノ酪酸、リジン、アスパラギン、D,L-アラニン、5-アミノ吉草酸、6-アミノカプロン酸、メチオニン、グルタミン酸、ヒスチジン、トリプトファンを用いた。また、アミノ酸類似化合物として、チオリンゴ酸を用いた。ビーカー内で水酸化ナトリウム2.5 mmol、アミノ酸系化合物2.5 mmolを水2 mLに溶かし、エタノール3mLを加えた。フラスコで塩化金酸四水和物0.32 mmolを水1 mLに溶かし、エタノール4mLを加えた。フラスコの塩化金酸溶液をビーカーに加え、エタノール6 mLで洗い出した。冷凍庫に一晩放置した。透明の上澄みを取り除き、少量の水で沈殿物を溶かし、エタノールで再沈殿させ、遠心分離器で上澄みを捨てた。エタノールで遠心洗浄を2回行った。錯体をろ取し、真空乾燥させた。 2. Amino acid compounds In addition to glycine, amino acids include β-alanine, 4-aminobutyric acid, lysine, asparagine, D, L-alanine, 5-aminovaleric acid, 6-aminocaproic acid, methionine, glutamic acid, histidine, and tryptophan. Using. Moreover, thiomalic acid was used as an amino acid analog. In a beaker, 2.5 mmol of sodium hydroxide and 2.5 mmol of an amino acid compound were dissolved in 2 mL of water, and 3 mL of ethanol was added. In a flask, 0.32 mmol of chloroauric acid tetrahydrate was dissolved in 1 mL of water, and 4 mL of ethanol was added. The chloroauric acid solution in the flask was added to a beaker and washed with 6 mL of ethanol. Left in the freezer overnight. The clear supernatant was removed, the precipitate was dissolved with a small amount of water, reprecipitated with ethanol, and the supernatant was discarded with a centrifuge. Centrifugal washing was performed twice with ethanol. The complex was collected by filtration and dried in vacuo.
金/アミノ酸系化合物錯体(グリシン、β-アラニン、4-アミノ酪酸、リジン、アスパラギン、5-アミノ吉草酸、6-アミノカプロン酸、メチオニン、グルタミン酸、ヒスチジン、トリプトファン、チオリンゴ酸)を用いて、以下の方法でシリカ担体上に担持させた。
Using gold / amino acid compound complexes (glycine, β-alanine, 4-aminobutyric acid, lysine, asparagine, 5-aminovaleric acid, 6-aminocaproic acid, methionine, glutamic acid, histidine, tryptophan, thiomalic acid) It was supported on a silica support by the method.
金/アミノ酸系化合物錯体(金10 mg相当)を乳鉢に入れ、水0.5 mLを加えて溶かし、そこに990 mgのSiO2を加えて30分間撹拌混和した。その後、乾燥させずに300℃で4時間空気焼成を行なった。
A gold / amino acid compound complex (equivalent to 10 mg of gold) was placed in a mortar, dissolved by adding 0.5 mL of water, 990 mg of SiO 2 was added thereto, and the mixture was stirred and mixed for 30 minutes. Thereafter, air baking was performed at 300 ° C. for 4 hours without drying.
各種の金/アミノ酸系化合物錯体を用いて調製したAu担持シリカ(Au/SiO2)をXRD測定した結果の一例として、β-アラニン(調製例1)、4-アミノ酪酸(調製例1)、リジン、又はアスパラギン(調製例1)と金との錯体を使用したAu/SiO2のXRD測定結果を図1に示す。また、各種の金/アミノ酸系化合物錯体を用いて調製したAu担持シリカ(Au/SiO2)の、38°付近の金のピークによる粒径を下記表2に示す。いずれも粒径の小さい金粒子を調製することができた。リジン及びメチオニンでは金の粒径が若干大きくなったが、これは、金/リジン錯体及び金/メチオニン錯体の水への溶解性が他の錯体よりも低く、溶け残りがある状態で含浸担持させたためであると考えられる。これら以外では、粒径が10nm未満と非常に小さい金粒子を調製することができた。
Examples of the results of XRD measurement of Au-supported silica (Au / SiO 2 ) prepared using various gold / amino acid compound complexes include β-alanine (Preparation Example 1), 4-aminobutyric acid (Preparation Example 1), FIG. 1 shows the result of XRD measurement of Au / SiO 2 using a complex of lysine or asparagine (Preparation Example 1) and gold. In addition, Table 2 shows the particle diameters of Au-supported silica (Au / SiO 2 ) prepared using various gold / amino acid compound complexes with a gold peak near 38 °. In either case, gold particles having a small particle size could be prepared. In lysine and methionine, the particle size of gold was slightly larger. This is because the solubility of gold / lysine complex and gold / methionine complex in water is lower than that of other complexes, and it is impregnated and supported in the state where there is any undissolved residue. This is probably because Other than these, gold particles having a very small particle size of less than 10 nm could be prepared.
遠心洗浄した金/β-アラニン錯体を水に溶かし、SiO2を加えて混ぜた後、真空凍結乾燥をしてから空気焼成した。XRDで測定したところ、粒径は9.1 nmだった。SiO2と混和後に乾燥をすることで粒径が大きくなったので、粒径の小さい金粒子を調製するためには乾燥させないことが必要であることを再確認した。
The centrifugally washed gold / β-alanine complex was dissolved in water, mixed with SiO 2 , vacuum lyophilized, and then air baked. The particle size was 9.1 nm as measured by XRD. It was reconfirmed that in order to prepare gold particles having a small particle size, it was necessary not to dry, since the particle size was increased by drying after mixing with SiO 2 .
3.担体の検討
シリカ担体の他、シリカアルミナ、活性炭及びモンモリロナイトへの含浸担持を検討した。金属/アミノ酸錯体は金/β-アラニン錯体を用いた。 3. Examination of support In addition to the silica support, impregnation support on silica alumina, activated carbon and montmorillonite was investigated. As the metal / amino acid complex, a gold / β-alanine complex was used.
シリカ担体の他、シリカアルミナ、活性炭及びモンモリロナイトへの含浸担持を検討した。金属/アミノ酸錯体は金/β-アラニン錯体を用いた。 3. Examination of support In addition to the silica support, impregnation support on silica alumina, activated carbon and montmorillonite was investigated. As the metal / amino acid complex, a gold / β-alanine complex was used.
<アルミニウム含有メソポーラスシリカ担体>
金/アミノ酸錯体(金10 mg相当)を乳鉢に入れ、水0.5 mLを加えて溶かし、そこに990 mgのシリカアルミナ(アルミニウム含有メソポーラスシリカMCM-41、シグマアルドリッチ社)を加えて30分間撹拌混和した。その後、乾燥させずに300℃で4時間空気焼成を行なうことで、Au担持アルミニウム含有メソポーラスシリカ(Au/Al-MCM-41-(A))を得た。透過型電子顕微鏡(TEM)画像から算出した金粒子の平均粒径は2.5 nmであり、シリカ担体の場合と同様に粒子径の小さい金粒子を担持させることができた。 <Aluminum-containing mesoporous silica support>
Place gold / amino acid complex (equivalent to 10 mg of gold) in a mortar, add 0.5 mL of water to dissolve, add 990 mg of silica alumina (aluminum-containing mesoporous silica MCM-41, Sigma-Aldrich), and stir and mix for 30 minutes. did. Thereafter, air calcination was carried out at 300 ° C. for 4 hours without drying to obtain Au-supported aluminum-containing mesoporous silica (Au / Al-MCM-41- (A)). The average particle diameter of the gold particles calculated from the transmission electron microscope (TEM) image was 2.5 nm, and gold particles having a small particle diameter could be supported as in the case of the silica carrier.
金/アミノ酸錯体(金10 mg相当)を乳鉢に入れ、水0.5 mLを加えて溶かし、そこに990 mgのシリカアルミナ(アルミニウム含有メソポーラスシリカMCM-41、シグマアルドリッチ社)を加えて30分間撹拌混和した。その後、乾燥させずに300℃で4時間空気焼成を行なうことで、Au担持アルミニウム含有メソポーラスシリカ(Au/Al-MCM-41-(A))を得た。透過型電子顕微鏡(TEM)画像から算出した金粒子の平均粒径は2.5 nmであり、シリカ担体の場合と同様に粒子径の小さい金粒子を担持させることができた。 <Aluminum-containing mesoporous silica support>
Place gold / amino acid complex (equivalent to 10 mg of gold) in a mortar, add 0.5 mL of water to dissolve, add 990 mg of silica alumina (aluminum-containing mesoporous silica MCM-41, Sigma-Aldrich), and stir and mix for 30 minutes. did. Thereafter, air calcination was carried out at 300 ° C. for 4 hours without drying to obtain Au-supported aluminum-containing mesoporous silica (Au / Al-MCM-41- (A)). The average particle diameter of the gold particles calculated from the transmission electron microscope (TEM) image was 2.5 nm, and gold particles having a small particle diameter could be supported as in the case of the silica carrier.
<活性炭担体>
金/β-アラニン錯体(金5 mg相当)を乳鉢に入れ、水0.5 mLを加えて撹拌し、そこに495 mgの活性炭(ケッチェンブラック、ライオン株式会社)を加えて30分撹拌混和した。その後、乾燥させずに300℃で30分空気焼成を行い、Au担持活性炭(Au/C-(A))を得た。活性炭担体上に担持された金粒子サイズは4.7nmであり、シリカ担体の場合と同様に粒子径の小さい金粒子を担持させることができた。 <Activated carbon carrier>
A gold / β-alanine complex (equivalent to 5 mg of gold) was placed in a mortar, 0.5 mL of water was added and stirred, 495 mg of activated carbon (Ketjen Black, Lion Co., Ltd.) was added, and the mixture was stirred and mixed for 30 minutes. Thereafter, air baking was performed at 300 ° C. for 30 minutes without drying to obtain Au-supported activated carbon (Au / C- (A)). The size of the gold particles supported on the activated carbon support was 4.7 nm, and gold particles having a small particle diameter could be supported as in the case of the silica support.
金/β-アラニン錯体(金5 mg相当)を乳鉢に入れ、水0.5 mLを加えて撹拌し、そこに495 mgの活性炭(ケッチェンブラック、ライオン株式会社)を加えて30分撹拌混和した。その後、乾燥させずに300℃で30分空気焼成を行い、Au担持活性炭(Au/C-(A))を得た。活性炭担体上に担持された金粒子サイズは4.7nmであり、シリカ担体の場合と同様に粒子径の小さい金粒子を担持させることができた。 <Activated carbon carrier>
A gold / β-alanine complex (equivalent to 5 mg of gold) was placed in a mortar, 0.5 mL of water was added and stirred, 495 mg of activated carbon (Ketjen Black, Lion Co., Ltd.) was added, and the mixture was stirred and mixed for 30 minutes. Thereafter, air baking was performed at 300 ° C. for 30 minutes without drying to obtain Au-supported activated carbon (Au / C- (A)). The size of the gold particles supported on the activated carbon support was 4.7 nm, and gold particles having a small particle diameter could be supported as in the case of the silica support.
<モンモリロナイト担体>
金/アミノ酸錯体(金10 mg相当)を乳鉢に入れ、水0.5 mLを加えて溶かし、そこに990 mgのモンモリロナイト(シグマアルドリッチ社)を加えて30分間撹拌混和した。その後、乾燥させずに300℃で4時間空気焼成を行なった。得られたAu担持モンモリロナイト(Au/Mont)の金粒子サイズは約10 nmであり(透過型電子顕微鏡(TEM)画像から算出)、シリカ担体の場合と同様にモンモリロナイトを担体として用いた場合も粒子径の小さい金粒子を担持させることができた。 <Montmorillonite carrier>
A gold / amino acid complex (equivalent to 10 mg of gold) was placed in a mortar, dissolved by adding 0.5 mL of water, 990 mg of montmorillonite (Sigma Aldrich) was added thereto, and the mixture was stirred and mixed for 30 minutes. Thereafter, air baking was performed at 300 ° C. for 4 hours without drying. The gold particle size of the obtained Au-supported montmorillonite (Au / Mont) is about 10 nm (calculated from a transmission electron microscope (TEM) image). Gold particles having a small diameter could be supported.
金/アミノ酸錯体(金10 mg相当)を乳鉢に入れ、水0.5 mLを加えて溶かし、そこに990 mgのモンモリロナイト(シグマアルドリッチ社)を加えて30分間撹拌混和した。その後、乾燥させずに300℃で4時間空気焼成を行なった。得られたAu担持モンモリロナイト(Au/Mont)の金粒子サイズは約10 nmであり(透過型電子顕微鏡(TEM)画像から算出)、シリカ担体の場合と同様にモンモリロナイトを担体として用いた場合も粒子径の小さい金粒子を担持させることができた。 <Montmorillonite carrier>
A gold / amino acid complex (equivalent to 10 mg of gold) was placed in a mortar, dissolved by adding 0.5 mL of water, 990 mg of montmorillonite (Sigma Aldrich) was added thereto, and the mixture was stirred and mixed for 30 minutes. Thereafter, air baking was performed at 300 ° C. for 4 hours without drying. The gold particle size of the obtained Au-supported montmorillonite (Au / Mont) is about 10 nm (calculated from a transmission electron microscope (TEM) image). Gold particles having a small diameter could be supported.
4.金微粒子担持体を用いたDMTS吸着実験-1
本発明の方法で調製される金属微粒子担持体の一用途として、含硫黄化合物の吸着除去剤を想定し、上記で調製した各種金微粒子担持体を用いて清酒の老香成分であるジメチルトリスルフィド(DMTS)(日本醸造協会誌, 101, 125-131, 2006)の吸着実験を行なった。 4). DMTS adsorption experiment using gold fine particle carrier-1
As one use of the metal fine particle carrier prepared by the method of the present invention, dimethyl trisulfide, which is an aroma component of sake using the various gold fine particle carriers prepared above, assuming an adsorption / removal agent for sulfur-containing compounds. (DMTS) (Japan Brewing Association Journal, 101, 125-131, 2006) was subjected to an adsorption experiment.
本発明の方法で調製される金属微粒子担持体の一用途として、含硫黄化合物の吸着除去剤を想定し、上記で調製した各種金微粒子担持体を用いて清酒の老香成分であるジメチルトリスルフィド(DMTS)(日本醸造協会誌, 101, 125-131, 2006)の吸着実験を行なった。 4). DMTS adsorption experiment using gold fine particle carrier-1
As one use of the metal fine particle carrier prepared by the method of the present invention, dimethyl trisulfide, which is an aroma component of sake using the various gold fine particle carriers prepared above, assuming an adsorption / removal agent for sulfur-containing compounds. (DMTS) (Japan Brewing Association Journal, 101, 125-131, 2006) was subjected to an adsorption experiment.
<吸着実験方法>
エタノールにDMTS及び内部標準のジエチレングリコールジメチルエーテルを加えて混合した。このうちの10μLをエタノール4 mLで希釈し、DMTS濃度を1.48×10-4 mmol(4.69 pm)に調整した。この溶液にAu/SiO2を加え、ガスクロマトグラフィーで吸着の様子を確認した。金微粒子担持体の使用量は、Au/DMTS=15~20になるように調整した。 <Adsorption experiment method>
DMTS and internal standard diethylene glycol dimethyl ether were added to ethanol and mixed. 10 μL of this was diluted with 4 mL of ethanol to adjust the DMTS concentration to 1.48 × 10 −4 mmol (4.69 pm). Au / SiO 2 was added to this solution, and the state of adsorption was confirmed by gas chromatography. The usage amount of the gold fine particle support was adjusted so that Au / DMTS = 15-20.
エタノールにDMTS及び内部標準のジエチレングリコールジメチルエーテルを加えて混合した。このうちの10μLをエタノール4 mLで希釈し、DMTS濃度を1.48×10-4 mmol(4.69 pm)に調整した。この溶液にAu/SiO2を加え、ガスクロマトグラフィーで吸着の様子を確認した。金微粒子担持体の使用量は、Au/DMTS=15~20になるように調整した。 <Adsorption experiment method>
DMTS and internal standard diethylene glycol dimethyl ether were added to ethanol and mixed. 10 μL of this was diluted with 4 mL of ethanol to adjust the DMTS concentration to 1.48 × 10 −4 mmol (4.69 pm). Au / SiO 2 was added to this solution, and the state of adsorption was confirmed by gas chromatography. The usage amount of the gold fine particle support was adjusted so that Au / DMTS = 15-20.
<結果>
(1) 上記1で調製した各種Au/SiO2のDMTS吸着能
金ナノ粒子のサイズが小さいAu/SiO2のうち、表1に示した条件[1]、[7]及び[8]のAu/SiO2、並びに市販の金ナノ粒子触媒(ハルタゴールド社製の1wt% Au/SiO2、金粒子サイズ7.1 nm)を用いて吸着実験を行なった結果を図2-1~図2-4に示す。また金ナノ粒子がやや大きいAu/SiO2のうち、条件[5]及び[9]のAu/SiO2、並びにDR法のAu/SiO2を用いて吸着実験を行なった結果を図2-5~図2-7に示す。担体上に担持された金粒子のサイズが小さいほどDMTSの吸着能が高い傾向が認められた。金箔で吸着実験を行なったところ、DMTSは全く吸着されなかった。 <Result>
(1) DMTS adsorption capacity of various Au / SiO 2 prepared in the above 1 Among Au / SiO 2 with small gold nanoparticle size, Au under the conditions [1], [7] and [8] shown in Table 1 Fig. 2-1 to Fig. 2-4 show the results of adsorption experiments using SiO2 / SiO 2 and a commercially available gold nanoparticle catalyst (Harta Gold 1wt% Au / SiO 2 , gold particle size 7.1 nm) Show. The results of adsorption experiments using Au / SiO 2 under the conditions [5] and [9] and Au / SiO 2 of the DR method among Au / SiO 2 with slightly larger gold nanoparticles are shown in FIG. 2-5. Figure 2-7 shows. It was observed that the smaller the size of the gold particles supported on the carrier, the higher the adsorption capacity of DMTS. When an adsorption experiment was performed with gold foil, DMTS was not adsorbed at all.
(1) 上記1で調製した各種Au/SiO2のDMTS吸着能
金ナノ粒子のサイズが小さいAu/SiO2のうち、表1に示した条件[1]、[7]及び[8]のAu/SiO2、並びに市販の金ナノ粒子触媒(ハルタゴールド社製の1wt% Au/SiO2、金粒子サイズ7.1 nm)を用いて吸着実験を行なった結果を図2-1~図2-4に示す。また金ナノ粒子がやや大きいAu/SiO2のうち、条件[5]及び[9]のAu/SiO2、並びにDR法のAu/SiO2を用いて吸着実験を行なった結果を図2-5~図2-7に示す。担体上に担持された金粒子のサイズが小さいほどDMTSの吸着能が高い傾向が認められた。金箔で吸着実験を行なったところ、DMTSは全く吸着されなかった。 <Result>
(1) DMTS adsorption capacity of various Au / SiO 2 prepared in the above 1 Among Au / SiO 2 with small gold nanoparticle size, Au under the conditions [1], [7] and [8] shown in Table 1 Fig. 2-1 to Fig. 2-4 show the results of adsorption experiments using SiO2 / SiO 2 and a commercially available gold nanoparticle catalyst (Harta Gold 1wt% Au / SiO 2 , gold particle size 7.1 nm) Show. The results of adsorption experiments using Au / SiO 2 under the conditions [5] and [9] and Au / SiO 2 of the DR method among Au / SiO 2 with slightly larger gold nanoparticles are shown in FIG. 2-5. Figure 2-7 shows. It was observed that the smaller the size of the gold particles supported on the carrier, the higher the adsorption capacity of DMTS. When an adsorption experiment was performed with gold foil, DMTS was not adsorbed at all.
(2) 上記2で調製したAu/SiO2のDMTS吸着能
金/β-アラニン錯体を用いたAu担持シリカAu/SiO2-(A)の結果を図3-1に、金/4-アミノ酪酸錯体を用いたAu担持シリカAu/SiO2-(GABA)の結果を図3-2に示す。いずれも良好なDMTS吸着能を有していた。 (2) DMTS adsorption capacity of Au / SiO 2 prepared in 2 above The results of Au-supported silica Au / SiO 2- (A) using a gold / β-alanine complex are shown in FIG. 3-1, and gold / 4-amino The results of Au-supported silica Au / SiO 2- (GABA) using a butyric acid complex are shown in FIG. All had good DMTS adsorption capacity.
金/β-アラニン錯体を用いたAu担持シリカAu/SiO2-(A)の結果を図3-1に、金/4-アミノ酪酸錯体を用いたAu担持シリカAu/SiO2-(GABA)の結果を図3-2に示す。いずれも良好なDMTS吸着能を有していた。 (2) DMTS adsorption capacity of Au / SiO 2 prepared in 2 above The results of Au-supported silica Au / SiO 2- (A) using a gold / β-alanine complex are shown in FIG. 3-1, and gold / 4-amino The results of Au-supported silica Au / SiO 2- (GABA) using a butyric acid complex are shown in FIG. All had good DMTS adsorption capacity.
(3) 上記3で調製した金微粒子担持体のDMTS吸着能
Au担持アルミニウム含有メソポーラスシリカ及びAu担持モンモリロナイトを用いたDMTS吸着実験の結果を図4-1及び図4-2にそれぞれ示す。いずれも良好なDMTS吸着能を有していた。 (3) DMTS adsorption capacity of gold fine particle support prepared in 3 above. The results of DMTS adsorption experiments using Au-supported aluminum-containing mesoporous silica and Au-supported montmorillonite are shown in FIGS. 4-1 and 4-2, respectively. All had good DMTS adsorption capacity.
Au担持アルミニウム含有メソポーラスシリカ及びAu担持モンモリロナイトを用いたDMTS吸着実験の結果を図4-1及び図4-2にそれぞれ示す。いずれも良好なDMTS吸着能を有していた。 (3) DMTS adsorption capacity of gold fine particle support prepared in 3 above. The results of DMTS adsorption experiments using Au-supported aluminum-containing mesoporous silica and Au-supported montmorillonite are shown in FIGS. 4-1 and 4-2, respectively. All had good DMTS adsorption capacity.
5.金微粒子担持体を用いたDMTS吸着実験-2
本発明の方法で調製される金属微粒子担持体の用途のさらなる例として、ガソリン等の液体燃料及び有機溶媒をはじめとする親油性の液体からの含硫黄化合物の吸着除去を想定し、金担持シリカを用いてヘキサンに添加したDMTSの吸着実験を行なった。 5. DMTS adsorption experiment using gold fine particle support-2
As a further example of the use of the fine metal particle support prepared by the method of the present invention, it is assumed that the sulfur-containing compound is adsorbed and removed from a liquid fuel such as gasoline and an oleophilic liquid such as an organic solvent. Was used to perform adsorption experiments of DMTS added to hexane.
本発明の方法で調製される金属微粒子担持体の用途のさらなる例として、ガソリン等の液体燃料及び有機溶媒をはじめとする親油性の液体からの含硫黄化合物の吸着除去を想定し、金担持シリカを用いてヘキサンに添加したDMTSの吸着実験を行なった。 5. DMTS adsorption experiment using gold fine particle support-2
As a further example of the use of the fine metal particle support prepared by the method of the present invention, it is assumed that the sulfur-containing compound is adsorbed and removed from a liquid fuel such as gasoline and an oleophilic liquid such as an organic solvent. Was used to perform adsorption experiments of DMTS added to hexane.
<方法>
(1) ヘキサンにDMTS及び内部標準としてトリデカンを加える
(2) (1)の溶液をヘキサンで希釈する(DMTS濃度: 6.0 ppm)
(3) (2)の試料4.0 mLにAu/SiO2(300℃, 0.5 h焼成, Au平均粒径5.1 nm)50.0 mgを加える
(4) GCで経時的にDMTS残量を測定する <Method>
(1) Add DMTS and tridecane as internal standard to hexane
(2) Dilute the solution of (1) with hexane (DMTS concentration: 6.0 ppm)
(3) Add 50.0 mg of Au / SiO 2 (300 ℃, calcined for 0.5 h, Au average particle size 5.1 nm) to 4.0 mL of the sample in (2)
(4) Measure DMTS remaining amount over time with GC
(1) ヘキサンにDMTS及び内部標準としてトリデカンを加える
(2) (1)の溶液をヘキサンで希釈する(DMTS濃度: 6.0 ppm)
(3) (2)の試料4.0 mLにAu/SiO2(300℃, 0.5 h焼成, Au平均粒径5.1 nm)50.0 mgを加える
(4) GCで経時的にDMTS残量を測定する <Method>
(1) Add DMTS and tridecane as internal standard to hexane
(2) Dilute the solution of (1) with hexane (DMTS concentration: 6.0 ppm)
(3) Add 50.0 mg of Au / SiO 2 (300 ℃, calcined for 0.5 h, Au average particle size 5.1 nm) to 4.0 mL of the sample in (2)
(4) Measure DMTS remaining amount over time with GC
<結果>
2回の実験の結果を図5-1(1回目)、図5-2(2回目)、及び表3に示す。6時間~24時間でヘキサン中のDMTSを完全に除去できた。これにより、本発明の方法で製造される金属微粒子担持体は親油性の有機化合物の液体に対しても良好なDMTS吸着能を発揮できることが確認された。 <Result>
The results of the two experiments are shown in FIG. 5-1 (first time), FIG. 5-2 (second time), and Table 3. DMTS in hexane was completely removed in 6 to 24 hours. As a result, it was confirmed that the metal fine particle carrier produced by the method of the present invention can exhibit a good DMTS adsorption ability even for a liquid of an oleophilic organic compound.
2回の実験の結果を図5-1(1回目)、図5-2(2回目)、及び表3に示す。6時間~24時間でヘキサン中のDMTSを完全に除去できた。これにより、本発明の方法で製造される金属微粒子担持体は親油性の有機化合物の液体に対しても良好なDMTS吸着能を発揮できることが確認された。 <Result>
The results of the two experiments are shown in FIG. 5-1 (first time), FIG. 5-2 (second time), and Table 3. DMTS in hexane was completely removed in 6 to 24 hours. As a result, it was confirmed that the metal fine particle carrier produced by the method of the present invention can exhibit a good DMTS adsorption ability even for a liquid of an oleophilic organic compound.
6.水素化反応触媒能の検討
酸化物担持金触媒は、水素化、酸化、C-C結合形成反応など各種の反応の触媒としても有効であることが知られており、金アミノ酸錯体を用いる新規含浸法により調製した金微粒子担持体も同様にこれらの反応の触媒として有効であると考えられる。そこで、各種金属酸化物を担体として新規含浸法により金属微粒子担持体を調製し、それらの水素化反応の触媒活性を調べた。 6). Examination of hydrogenation reaction catalytic ability Oxide-supported gold catalysts are known to be effective as catalysts for various reactions such as hydrogenation, oxidation, and CC bond formation reactions. The prepared gold fine particle support is also considered to be effective as a catalyst for these reactions. Therefore, metal fine particle carriers were prepared by a novel impregnation method using various metal oxides as carriers, and the catalytic activity of their hydrogenation reaction was investigated.
酸化物担持金触媒は、水素化、酸化、C-C結合形成反応など各種の反応の触媒としても有効であることが知られており、金アミノ酸錯体を用いる新規含浸法により調製した金微粒子担持体も同様にこれらの反応の触媒として有効であると考えられる。そこで、各種金属酸化物を担体として新規含浸法により金属微粒子担持体を調製し、それらの水素化反応の触媒活性を調べた。 6). Examination of hydrogenation reaction catalytic ability Oxide-supported gold catalysts are known to be effective as catalysts for various reactions such as hydrogenation, oxidation, and CC bond formation reactions. The prepared gold fine particle support is also considered to be effective as a catalyst for these reactions. Therefore, metal fine particle carriers were prepared by a novel impregnation method using various metal oxides as carriers, and the catalytic activity of their hydrogenation reaction was investigated.
<シリカ担体>
金/グリシン錯体を用いた含浸法によるAu担持シリカ(1wt% Au/SiO2-(G-3))は、上記表1に示した条件[1](基準条件)にて調製した。
金/β-アラニン錯体を用いた含浸法によるAu担持シリカ(1wt% Au/SiO2-(A))は、上記2の通りに調製した。
4wt% Au/SiO2-(A)は次の通りに調製した。金/β-アラニン錯体(金40 mg相当)を乳鉢に入れ、水0.5 mLを加えて溶かし、そこに960 mgのSi02を加えて30分間撹拌混和した。その後、乾燥させずに300℃で4時間空気焼成を行なった。 <Silica support>
Au-supported silica (1 wt% Au / SiO 2- (G-3)) by an impregnation method using a gold / glycine complex was prepared under the conditions [1] (reference conditions) shown in Table 1 above.
Au-supported silica (1 wt% Au / SiO 2- (A)) by an impregnation method using a gold / β-alanine complex was prepared as described above.
4 wt% Au / SiO 2- (A) was prepared as follows. A gold / β-alanine complex (equivalent to 40 mg of gold) was placed in a mortar, dissolved by adding 0.5 mL of water, 960 mg of SiO 2 was added thereto, and the mixture was stirred and mixed for 30 minutes. Thereafter, air baking was performed at 300 ° C. for 4 hours without drying.
金/グリシン錯体を用いた含浸法によるAu担持シリカ(1wt% Au/SiO2-(G-3))は、上記表1に示した条件[1](基準条件)にて調製した。
金/β-アラニン錯体を用いた含浸法によるAu担持シリカ(1wt% Au/SiO2-(A))は、上記2の通りに調製した。
4wt% Au/SiO2-(A)は次の通りに調製した。金/β-アラニン錯体(金40 mg相当)を乳鉢に入れ、水0.5 mLを加えて溶かし、そこに960 mgのSi02を加えて30分間撹拌混和した。その後、乾燥させずに300℃で4時間空気焼成を行なった。 <Silica support>
Au-supported silica (1 wt% Au / SiO 2- (G-3)) by an impregnation method using a gold / glycine complex was prepared under the conditions [1] (reference conditions) shown in Table 1 above.
Au-supported silica (1 wt% Au / SiO 2- (A)) by an impregnation method using a gold / β-alanine complex was prepared as described above.
4 wt% Au / SiO 2- (A) was prepared as follows. A gold / β-alanine complex (equivalent to 40 mg of gold) was placed in a mortar, dissolved by adding 0.5 mL of water, 960 mg of SiO 2 was added thereto, and the mixture was stirred and mixed for 30 minutes. Thereafter, air baking was performed at 300 ° C. for 4 hours without drying.
<酸化チタン担体>
金/β-アラニン錯体(金10 mg相当)を乳鉢に入れ、水0.5 mLを加えて溶かし、そこに990 mgの酸化チタン(P-25、日本アエロジル社)を加えて30分間撹拌混和した。その後、乾燥させずに300℃で4時間空気焼成を行ない、Au担持酸化チタン(Au/TiO2-(A))を得た。透過型電子顕微鏡(TEM)画像から算出した金粒子の平均粒径は2.5 nmであり、シリカ担体の場合と同様に粒子径の小さい金粒子を担持させることができた。 <Titanium oxide carrier>
A gold / β-alanine complex (equivalent to 10 mg of gold) was placed in a mortar, dissolved by adding 0.5 mL of water, 990 mg of titanium oxide (P-25, Nippon Aerosil Co., Ltd.) was added thereto, and the mixture was stirred and mixed for 30 minutes. Thereafter, air baking was performed at 300 ° C. for 4 hours without drying to obtain Au-supported titanium oxide (Au / TiO 2- (A)). The average particle diameter of the gold particles calculated from the transmission electron microscope (TEM) image was 2.5 nm, and gold particles having a small particle diameter could be supported as in the case of the silica carrier.
金/β-アラニン錯体(金10 mg相当)を乳鉢に入れ、水0.5 mLを加えて溶かし、そこに990 mgの酸化チタン(P-25、日本アエロジル社)を加えて30分間撹拌混和した。その後、乾燥させずに300℃で4時間空気焼成を行ない、Au担持酸化チタン(Au/TiO2-(A))を得た。透過型電子顕微鏡(TEM)画像から算出した金粒子の平均粒径は2.5 nmであり、シリカ担体の場合と同様に粒子径の小さい金粒子を担持させることができた。 <Titanium oxide carrier>
A gold / β-alanine complex (equivalent to 10 mg of gold) was placed in a mortar, dissolved by adding 0.5 mL of water, 990 mg of titanium oxide (P-25, Nippon Aerosil Co., Ltd.) was added thereto, and the mixture was stirred and mixed for 30 minutes. Thereafter, air baking was performed at 300 ° C. for 4 hours without drying to obtain Au-supported titanium oxide (Au / TiO 2- (A)). The average particle diameter of the gold particles calculated from the transmission electron microscope (TEM) image was 2.5 nm, and gold particles having a small particle diameter could be supported as in the case of the silica carrier.
<酸化タングステン担体>
金/β-アラニン錯体(金10 mg相当)を乳鉢に入れ、水0.5 mLを加えて溶かし、そこに990 mgの酸化タングステン(和光純薬工業社)を加えて30分間撹拌混和した。その後、乾燥させずに300℃で4時間空気焼成を行ない、Au担持酸化タングステン(Au/WO3-(A))を得た。 <Tungsten oxide carrier>
A gold / β-alanine complex (equivalent to 10 mg of gold) was placed in a mortar, dissolved by adding 0.5 mL of water, 990 mg of tungsten oxide (Wako Pure Chemical Industries, Ltd.) was added thereto, and the mixture was stirred and mixed for 30 minutes. Thereafter, air baking was performed at 300 ° C. for 4 hours without drying to obtain Au-supported tungsten oxide (Au / WO 3- (A)).
金/β-アラニン錯体(金10 mg相当)を乳鉢に入れ、水0.5 mLを加えて溶かし、そこに990 mgの酸化タングステン(和光純薬工業社)を加えて30分間撹拌混和した。その後、乾燥させずに300℃で4時間空気焼成を行ない、Au担持酸化タングステン(Au/WO3-(A))を得た。 <Tungsten oxide carrier>
A gold / β-alanine complex (equivalent to 10 mg of gold) was placed in a mortar, dissolved by adding 0.5 mL of water, 990 mg of tungsten oxide (Wako Pure Chemical Industries, Ltd.) was added thereto, and the mixture was stirred and mixed for 30 minutes. Thereafter, air baking was performed at 300 ° C. for 4 hours without drying to obtain Au-supported tungsten oxide (Au / WO 3- (A)).
<酸化ジルコニウム担体>
金/β-アラニン錯体(金10 mg相当)を乳鉢に入れ、水0.5 mLを加えて溶かし、そこに990 mgの酸化ジルコニウム(触媒学会参照触媒(第一稀元素化学工業株式会社)、品番:JRC-ZRO-4)を加えて30分間撹拌混和した。その後、乾燥させずに300℃で4時間空気焼成を行ない、Au担持酸化ジルコニウム(Au/ZrO2-(A))を得た。 <Zirconium oxide support>
Place a gold / β-alanine complex (equivalent to 10 mg of gold) in a mortar, add 0.5 mL of water to dissolve it, and dissolve 990 mg of zirconium oxide (Catalyst Society Reference Catalyst (Daiichi Rare Element Chemical Co., Ltd.)) JRC-ZRO-4) was added and mixed with stirring for 30 minutes. Then, air baking was performed at 300 ° C. for 4 hours without drying to obtain Au-supported zirconium oxide (Au / ZrO 2- (A)).
金/β-アラニン錯体(金10 mg相当)を乳鉢に入れ、水0.5 mLを加えて溶かし、そこに990 mgの酸化ジルコニウム(触媒学会参照触媒(第一稀元素化学工業株式会社)、品番:JRC-ZRO-4)を加えて30分間撹拌混和した。その後、乾燥させずに300℃で4時間空気焼成を行ない、Au担持酸化ジルコニウム(Au/ZrO2-(A))を得た。 <Zirconium oxide support>
Place a gold / β-alanine complex (equivalent to 10 mg of gold) in a mortar, add 0.5 mL of water to dissolve it, and dissolve 990 mg of zirconium oxide (Catalyst Society Reference Catalyst (Daiichi Rare Element Chemical Co., Ltd.)) JRC-ZRO-4) was added and mixed with stirring for 30 minutes. Then, air baking was performed at 300 ° C. for 4 hours without drying to obtain Au-supported zirconium oxide (Au / ZrO 2- (A)).
<酸化アルミニウム担体>
金/β-アラニン錯体(金10 mg相当)を乳鉢に入れ、水0.5 mLを加えて溶かし、そこに990 mgの酸化ジルコニウム(触媒学会参照触媒(水沢化学工業株式会社)、品番:JRC-ALO-5)を加えて30分間撹拌混和した。その後、乾燥させずに300℃で4時間空気焼成を行ない、Au担持酸化アルミニウム(Au/Al2O3-(A))を得た。 <Aluminum oxide carrier>
Place a gold / β-alanine complex (equivalent to 10 mg of gold) in a mortar, add 0.5 mL of water to dissolve it, and dissolve 990 mg of zirconium oxide (Catalyst Society Reference Catalyst (Mizusawa Chemical Co., Ltd.), product number: JRC-ALO -5) was added and mixed with stirring for 30 minutes. Thereafter, air baking was performed at 300 ° C. for 4 hours without drying to obtain Au-supported aluminum oxide (Au / Al 2 O 3- (A)).
金/β-アラニン錯体(金10 mg相当)を乳鉢に入れ、水0.5 mLを加えて溶かし、そこに990 mgの酸化ジルコニウム(触媒学会参照触媒(水沢化学工業株式会社)、品番:JRC-ALO-5)を加えて30分間撹拌混和した。その後、乾燥させずに300℃で4時間空気焼成を行ない、Au担持酸化アルミニウム(Au/Al2O3-(A))を得た。 <Aluminum oxide carrier>
Place a gold / β-alanine complex (equivalent to 10 mg of gold) in a mortar, add 0.5 mL of water to dissolve it, and dissolve 990 mg of zirconium oxide (Catalyst Society Reference Catalyst (Mizusawa Chemical Co., Ltd.), product number: JRC-ALO -5) was added and mixed with stirring for 30 minutes. Thereafter, air baking was performed at 300 ° C. for 4 hours without drying to obtain Au-supported aluminum oxide (Au / Al 2 O 3- (A)).
<水素化反応>
50 mL高圧反応容器に4-ニトロスチレン(1 mmol)、酢酸エチル2 mL、トリグリム60.5 mg (GC定量用の内部標準)、及び触媒として金微粒子担持体10 mgを入れ、2 MPaの水素で1回置換したのち、2 MPaの水素圧をかけ、100℃で24時間撹拌した。冷却後、反応容器を開け、ガスクロマトグラフにて生成物を分析した。反応後の4-ニトロスチレンの残存量も分析し、生成物への変換率を算出した。
変換率(%)=(1-n)/1×100
n: 反応後(1 day後)に残った4-ニトロスチレンの物質量(mmol) <Hydrogenation reaction>
Place 4-nitrostyrene (1 mmol), ethyl acetate (2 mL), triglyme (60.5 mg) (internal standard for GC determination) and gold fine particle support (10 mg) as a catalyst in a 50 mL high-pressure reaction vessel. After the replacement, the hydrogen pressure of 2 MPa was applied and the mixture was stirred at 100 ° C. for 24 hours. After cooling, the reaction vessel was opened and the product was analyzed with a gas chromatograph. The residual amount of 4-nitrostyrene after the reaction was also analyzed, and the conversion rate to the product was calculated.
Conversion rate (%) = (1-n) / 1 x 100
n: Amount of 4-nitrostyrene remaining after reaction (after 1 day) (mmol)
50 mL高圧反応容器に4-ニトロスチレン(1 mmol)、酢酸エチル2 mL、トリグリム60.5 mg (GC定量用の内部標準)、及び触媒として金微粒子担持体10 mgを入れ、2 MPaの水素で1回置換したのち、2 MPaの水素圧をかけ、100℃で24時間撹拌した。冷却後、反応容器を開け、ガスクロマトグラフにて生成物を分析した。反応後の4-ニトロスチレンの残存量も分析し、生成物への変換率を算出した。
変換率(%)=(1-n)/1×100
n: 反応後(1 day後)に残った4-ニトロスチレンの物質量(mmol) <Hydrogenation reaction>
Place 4-nitrostyrene (1 mmol), ethyl acetate (2 mL), triglyme (60.5 mg) (internal standard for GC determination) and gold fine particle support (10 mg) as a catalyst in a 50 mL high-pressure reaction vessel. After the replacement, the hydrogen pressure of 2 MPa was applied and the mixture was stirred at 100 ° C. for 24 hours. After cooling, the reaction vessel was opened and the product was analyzed with a gas chromatograph. The residual amount of 4-nitrostyrene after the reaction was also analyzed, and the conversion rate to the product was calculated.
Conversion rate (%) = (1-n) / 1 x 100
n: Amount of 4-nitrostyrene remaining after reaction (after 1 day) (mmol)
結果を表4に示す。1 wt% Au/SiO2触媒はビニル基が選択的に水素化された生成物Aを54~59%収率で与えた(番号1、2)。酸化ジルコニウムに担持された金触媒も同様の傾向を示した。(番号6)。その一方で、4 wt% Au/SiO2触媒はニトロ基が選択的に水素化された生成物Bおよび、両方の官能基が水素化された生成物Cを、それぞれ47%と34%で与えた(番号3)。また、酸化チタン、酸化アルミニウムに担持された金触媒はニトロ基が選択的に水素化された生成物Bを選択的に与えた。(番号5、7)。
The results are shown in Table 4. 1 wt% Au / SiO 2 catalyst vinyl group gave in selectively hydrogenated product A of 54 to 59% yield (numbers 1 and 2). The gold catalyst supported on zirconium oxide showed the same tendency. (Number 6). On the other hand, the 4 wt% Au / SiO 2 catalyst gives 47% and 34% of product B in which nitro groups are selectively hydrogenated and product C in which both functional groups are hydrogenated, respectively. (Number 3). Further, the gold catalyst supported on titanium oxide and aluminum oxide selectively gave the product B in which the nitro group was selectively hydrogenated. (Numbers 5, 7).
7.金/β-アラニン錯体の構造解析
錠剤成型した所定量の試料をSPring-8 BL14B2の光路上にセットし、透過法により Au L3-edge XAFSを測定した。測定には、Si(311)二結晶モノクロメータとイオンチャンバー検出器を用い、データは、REX2000(リガク)により解析した。 7). Structural analysis of gold / β-alanine complex A predetermined amount of a tablet-molded sample was set on the optical path of SPring-8 BL14B2, and Au L3-edge XAFS was measured by the transmission method. For the measurement, a Si (311) double crystal monochromator and an ion chamber detector were used, and the data were analyzed by REX2000 (Rigaku).
錠剤成型した所定量の試料をSPring-8 BL14B2の光路上にセットし、透過法により Au L3-edge XAFSを測定した。測定には、Si(311)二結晶モノクロメータとイオンチャンバー検出器を用い、データは、REX2000(リガク)により解析した。 7). Structural analysis of gold / β-alanine complex A predetermined amount of a tablet-molded sample was set on the optical path of SPring-8 BL14B2, and Au L3-edge XAFS was measured by the transmission method. For the measurement, a Si (311) double crystal monochromator and an ion chamber detector were used, and the data were analyzed by REX2000 (Rigaku).
金/β-アラニン錯体のX線吸収微細構造(XAFS)スペクトル(図6)では、11922 eV付近にAu 2p3/2から5dおよび6s軌道への遷移に相当する特徴的なホワイトラインが観測された。また、EXAFS振動スペクトル(図7)は、標準試料として測定したAu2O3のスペクトルと類似していた。このことから、金/β-アラニン錯体は3価Auが中心金属となった平面4配位状態であることが示唆された。さらに、EXAFSスペクトルフーリエ変換(図8)のカーブフィッティング解析の結果、金/β-アラニン錯体の分子構造は、β-アラニンが2分子、もしくはβ-アラニン1分子と水酸基2分子が配位した単核錯体であることが示唆された。
In the X-ray absorption fine structure (XAFS) spectrum of the gold / β-alanine complex (Fig. 6), a characteristic white line corresponding to the transition from Au 2p 3/2 to 5d and 6s orbitals was observed near 11922 eV. It was. The EXAFS vibration spectrum (FIG. 7) was similar to the spectrum of Au 2 O 3 measured as a standard sample. This suggests that the gold / β-alanine complex is in a planar four-coordinate state in which trivalent Au is the central metal. Furthermore, as a result of curve fitting analysis of EXAFS spectral Fourier transform (FIG. 8), the molecular structure of the gold / β-alanine complex is a single molecule in which two β-alanine molecules or one β-alanine molecule and two hydroxyl groups are coordinated. It was suggested to be a nuclear complex.
Claims (13)
- 後周期遷移金属/アミノ酸錯体及び後周期遷移金属/アミノ酸類似化合物錯体からなる群より選択される少なくとも1種の錯体の溶液と担体を混和して、前記少なくとも1種の錯体を担体に含浸させる工程、及び
錯体含浸後の担体を焼成する工程
を含む、後周期遷移金属微粒子担持体の製造方法。 Mixing at least one complex solution selected from the group consisting of late-period transition metal / amino acid complex and late-period transition metal / amino acid analog compound complex with a carrier and impregnating the carrier with the at least one complex; And a method for producing a late transition metal fine particle carrier, comprising the step of firing the carrier after impregnation with the complex. - 前記少なくとも1種の錯体が、少なくとも1種の後周期遷移金属/アミノ酸錯体である、請求項1記載の方法。 The method of claim 1, wherein the at least one complex is at least one late transition metal / amino acid complex.
- 前記後周期遷移金属が、金、銀、白金、パラジウム、ルテニウム、ロジウム、オスミウム、イリジウム、鉄、コバルト、ニッケル、銅、亜鉛、及び鉛からなる群より選択される少なくとも1種である、請求項1又は2記載の方法。 The late transition metal is at least one selected from the group consisting of gold, silver, platinum, palladium, ruthenium, rhodium, osmium, iridium, iron, cobalt, nickel, copper, zinc, and lead. The method according to 1 or 2.
- 前記後周期遷移金属が金である、請求項3記載の方法。 4. The method of claim 3, wherein the late transition metal is gold.
- 前記担体が、ケイ素材料、炭素材料、金属酸化物、粘土、合成又は天然ポリマー、炭酸塩、多孔性配位高分子及び窒化ホウ素からなる群より選択される少なくとも1種である、請求項1ないし4のいずれか1項に記載の方法。 The carrier is at least one selected from the group consisting of silicon materials, carbon materials, metal oxides, clays, synthetic or natural polymers, carbonates, porous coordination polymers and boron nitride. 5. The method according to any one of 4 above.
- 前記アミノ酸は、アルギニン、ヒスチジン、リジン、アスパラギン酸、グルタミン酸、アラニン、グリシン、ロイシン、バリン、イソロイシン、セリン、スレオニン、フェニルアラニン、トリプトファン、チロシン、シスチン又はシステイン、グルタミン、アスパラギン、プロリン、メチオニン、β-アラニン、γ-アミノ酪酸、カルニチン、γ-アミノレブリン酸、及びγ-アミノ吉草酸からなる群より選択される少なくとも1種である、請求項1ないし5のいずれか1項に記載の方法。 The amino acids are arginine, histidine, lysine, aspartic acid, glutamic acid, alanine, glycine, leucine, valine, isoleucine, serine, threonine, phenylalanine, tryptophan, tyrosine, cystine or cysteine, glutamine, asparagine, proline, methionine, β-alanine. The method according to any one of claims 1 to 5, which is at least one selected from the group consisting of γ-aminobutyric acid, carnitine, γ-aminolevulinic acid, and γ-aminovaleric acid.
- 前記アミノ酸は、アルギニン、ヒスチジン、リジン、アスパラギン酸、グルタミン酸、アラニン、グリシン、ロイシン、バリン、イソロイシン、セリン、スレオニン、フェニルアラニン、トリプトファン、チロシン、シスチン又はシステイン、グルタミン、アスパラギン、プロリン、メチオニン、β-アラニン、γ-アミノ酪酸、カルニチン、γ-アミノレブリン酸、γ-アミノ吉草酸、δ-アミノ吉草酸、及びε-アミノカプロン酸からなる群より選択される少なくとも1種である、請求項1ないし5のいずれか1項に記載の方法。 The amino acids are arginine, histidine, lysine, aspartic acid, glutamic acid, alanine, glycine, leucine, valine, isoleucine, serine, threonine, phenylalanine, tryptophan, tyrosine, cystine or cysteine, glutamine, asparagine, proline, methionine, β-alanine. 6. The method according to claim 1, which is at least one selected from the group consisting of γ-aminobutyric acid, carnitine, γ-aminolevulinic acid, γ-aminovaleric acid, δ-aminovaleric acid, and ε-aminocaproic acid. The method according to claim 1.
- 前記アミノ酸類似化合物は、
アミノ酸分子の少なくとも1個のアミノ基がスルフヒドリル基に置き換わった化合物;
アミノ酸分子の少なくとも1個のアミノ基に少なくとも1個のアルキル基が結合した化合物;
アミノ酸分子の主鎖及び側鎖を構成する炭素原子の少なくとも1個が窒素原子、酸素原子及び硫黄原子から選択される少なくとも1つに置き換わった化合物;並びに
アミノ酸分子の主鎖及び側鎖を構成する炭素原子の少なくとも1個に、アルキル基、水酸基及びハロゲン原子からなる群より選択される少なくとも1つが結合した化合物
からなる群より選択される少なくとも1種である、請求項1、3ないし7のいずれか1項に記載の方法。 The amino acid analog is
Compounds in which at least one amino group of the amino acid molecule is replaced by a sulfhydryl group;
A compound in which at least one alkyl group is bonded to at least one amino group of an amino acid molecule;
A compound in which at least one carbon atom constituting the main chain and side chain of the amino acid molecule is replaced by at least one selected from a nitrogen atom, an oxygen atom and a sulfur atom; and constituting the main chain and side chain of the amino acid molecule 8. The method according to claim 1, which is at least one selected from the group consisting of compounds in which at least one selected from the group consisting of an alkyl group, a hydroxyl group and a halogen atom is bonded to at least one carbon atom. The method according to claim 1. - 前記アミノ酸類似化合物は、チオリンゴ酸、p-クロロフェニルアラニン、β-クロロアラニン、ヒドロキシプロリン、ヒドロキシリジン、及びサルコシンからなる群より選択される少なくとも1種である、請求項8記載の方法。 The method according to claim 8, wherein the amino acid analog compound is at least one selected from the group consisting of thiomalic acid, p-chlorophenylalanine, β-chloroalanine, hydroxyproline, hydroxylysine, and sarcosine.
- 錯体含浸後の担体を乾燥させる工程を経ずに焼成する、請求項1ないし9のいずれか1項に記載の方法。 The method according to any one of claims 1 to 9, wherein the carrier after the complex impregnation is baked without passing through the step of drying.
- 前記微粒子は、平均粒径が50nm以下である、請求項1ないし10のいずれか1項に記載の方法。 The method according to any one of claims 1 to 10, wherein the fine particles have an average particle size of 50 nm or less.
- 後周期遷移金属にアミノ酸(ただしグリシン、ヒスチジン及びトリプトファンを除く)又はアミノ酸類似化合物が配位してなる金属錯体。 A metal complex in which an amino acid (excluding glycine, histidine and tryptophan) or an amino acid analog compound is coordinated to a late transition metal.
- 後周期遷移金属にアミノ酸が配位してなる請求項12記載の金属錯体。 The metal complex according to claim 12, wherein an amino acid is coordinated to the late transition metal.
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CN110560160B (en) * | 2019-09-18 | 2020-11-20 | 河南大学 | Preparation method and application of Phe @ CuNCs composite material |
CN113457633A (en) * | 2021-07-06 | 2021-10-01 | 福州大学 | Polyphenol-modified gamma-alumina-based porous carbon composite material, and preparation method and application thereof |
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