WO2010110447A1 - Agrégat d'or supporté dans de la silice mésoporeuse, catalyseur comprenant ledit agrégat, et procédé de production de celui-ci - Google Patents

Agrégat d'or supporté dans de la silice mésoporeuse, catalyseur comprenant ledit agrégat, et procédé de production de celui-ci Download PDF

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WO2010110447A1
WO2010110447A1 PCT/JP2010/055434 JP2010055434W WO2010110447A1 WO 2010110447 A1 WO2010110447 A1 WO 2010110447A1 JP 2010055434 W JP2010055434 W JP 2010055434W WO 2010110447 A1 WO2010110447 A1 WO 2010110447A1
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mesoporous silica
gold
supported
range
silica
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達哉 佃
永梅 劉
寛規 角山
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国立大学法人北海道大学
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/0325—Noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/618—Surface area more than 1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating

Definitions

  • the present invention relates to a mesoporous silica-supported gold cluster, a catalyst using the same, and a method for producing the same.
  • Nano-sized gold catalysts supported on metal oxides have attracted attention.
  • silica By immobilizing the gold catalyst on the carrier, there is an advantage that it can be recovered from the reaction system and reused.
  • silica can be used as a support, there is an advantage that a gold cluster catalyst which is superior in safety and economy can be produced.
  • Mono-dispersed gold clusters of less than 5 nm supported on silica are ideal materials for studying the intrinsic catalytic activity of gold clusters. This is because silica is catalytically inactive and its interaction with clusters is relatively weak.
  • Non-Patent Documents 1 and 2 such as coprecipitation method (DP) and impregnation support method (IP) cannot be used. .
  • Non-patent Document 3 As a method of supporting the gold cluster on the metal oxide, monodispersed gold nanoparticles (average particle size 3.5 ⁇ 0.5, 6.3 ⁇ 0.5, 8.2 ⁇ 0.9 nm) protected with alkanethiol are prepared in advance, and this is prepared using an organic solvent ( It is adsorbed on metal oxides (tungsten oxide, soot zeolite, silica, titania, zirconia, tin oxide, iridium oxide, iron oxide, alumina, zinc oxide, nickel oxide) in chloroform and dichloromethane).
  • metal oxides tungsten oxide, soot zeolite, silica, titania, zirconia, tin oxide, iridium oxide, iron oxide, alumina, zinc oxide, nickel oxide
  • a method of preparing supported monodispersed gold nanoparticles by firing for a time is known (Non-patent Document 3). In Non-Patent Document 3, the catalytic activity of the supported mono
  • a gold 55-mer (Au55, particle size 1.4 nm) protected with triphenylphosphine was synthesized in advance and adsorbed onto silica in an organic solvent (dichloromethane).
  • a method of preparing supported monodispersed gold nanoparticles by firing for a time is known (Non-Patent Document 4).
  • the average particle size was 1.4 nm.
  • the catalytic activity for partial oxidation of styrene in toluene at 100 ° C. was evaluated.
  • Patent Document 1 discloses a composite of cerium-containing mesoporous silica and noble metal ultrafine particles, a method for producing the composite, a method for oxidative removal of trace carbon monoxide using the composite as a catalyst, and an alcohol.
  • a method for the synthesis of ketones by oxidative dehydrogenation of the class is disclosed.
  • the composite is characterized in that ultrafine gold particles are supported on mesoporous silica containing cerium, and the diameter of the ultrafine particles is in the range of 0.5 to 5 nm, and the total number of particles is almost the same. Is included.
  • Example 2 as a result of measuring the particle size of the gold particles in the catalyst used in Example 1, the range of 0 to 0.5 nm is 1% of the total number of particles, and the range of 0.5 to 1 nm. Is 16% of the total number of particles, 51% of the total number of particles in the range of 1 to 1.5 nm, 21% of the total number of particles in the range of 1.5 to 2.0 nm, 2.0 to 2.5 nm The range was 9% of the total number of particles, and the range of 2.5 to 3.0 nm was 2% of the total number of particles.
  • Patent Document 1 describes a method of supporting ultrafine gold particles on mesoporous silica containing cerium.
  • an alkaline solution is added to an aqueous solution of chloroauric acid to adjust the pH value to a range of 7.0 or more and less than 10.0, thereby changing chloroauric acid to a state in which hydroxide ions are coordinated.
  • the surface of the mesoporous silica is a precursor of the ultrafine gold particles with an electrical affinity.
  • a method of adsorbing a gold complex coordinated with hydroxide ions is used.
  • Patent Document 1 The entire description of Patent Document 1 and Non-Patent Documents 1 to 8 is specifically incorporated herein by reference.
  • Non-patent Document 5 Non-patent Document 5
  • silica one of the most common catalyst supports, is difficult to prepare, so there is no information on the size effect of the gold catalyst.
  • the general methods such as the coprecipitation method and the impregnation support method described above, it is impossible to suppress the particle size to 5 nm or less, and a wide distribution occurs in the size.
  • the gold ultrafine particles are supported on mesoporous silica containing cerium, so that the diameter of the gold ultrafine particles is within the range of 0.5 to 5 nm, and most of the total number of particles is included.
  • a complex is provided.
  • the number of ultrafine gold particles is 17% of the total number of particles when the diameter is in the range of 0 to 1 nm, whereas the total number of gold particles is within the range of 1 to 3.0 nm. 83%. That is, even with this method, it is still difficult to make the size of gold ultrafine particles smaller than 1 nm.
  • an object of the present invention is to provide a method for preparing a silica-supported gold cluster in the sub-nanometer to several nanometer region, and thereby to provide a sub-nanometer silica-supported gold cluster that has never been obtained. Furthermore, another object of the present invention is to provide a catalyst using a silica-supported gold cluster in the sub-nanometer range to a few nanometer range.
  • the present inventors have made various studies to achieve the above object, and as a result, by using triphenylphosphine-protected gold 11-mer (Au 11 , particle size 0.8 nm) as a starting material, sub-nanometers to several nanometers are obtained. We have found that a silica-supported gold cluster in the region can be prepared and completed the present invention.
  • the present invention for achieving the above object is as follows.
  • [1] A composite of gold clusters and mesoporous silica composed of mesoporous silica in which gold clusters having a particle size in the range of 0.8 to 1.0 nm are supported in pores.
  • [2] The composite according to [1], wherein the mesoporous silica has a pore diameter in the range of 2 to 50 nm.
  • Au 11 : TTP is the production method according to [7], wherein at least one of or both of [Au 11 (TPP) 8 Cl 2 ] + and Au 11 (TPP) 7 Cl 3 is included. [9] The production method according to [7] or [8], wherein Au 11 : TTP is mixed in an amount of 0.1 to 2.5 parts by mass with respect to 100 parts by mass of mesoporous silica. [Ten] The method according to any one of [7] to [9], wherein the firing is performed at a temperature in the range of 180 to 220 ° C.
  • the present invention it is possible to provide a method for preparing a silica-supported gold cluster in the sub-nanometer to several nanometer region, thereby providing a sub-nanometer silica-supported gold cluster that has not been obtained conventionally.
  • a catalyst using a silica-supported gold cluster in the sub-nanometer to several nanometer range it is possible to provide a method for preparing a silica-supported gold cluster in the sub-nanometer to several nanometer region.
  • FIG. 1 shows the results of thermogravimetric analysis of gold 11-mer (Au 11 ) (Au 11 : TPP) synthesized in Reference Example 1.
  • FIG. 2 shows the results of examining the dependence of the firing time on the size of the gold cluster by diffuse reflectance spectroscopy when SBA-15 shown in Reference Example 2 is used as the carrier.
  • FIG. 3 shows the case where SBA-15 (Reference Example 2), MCF (Reference Example 3) and HMS (Reference Example 4) are used as carriers and silica (SiO 2 ) is used as a reference, and the firing time is 2 hours. It is the result of having investigated the dependence of the support
  • FIG. 1 shows the results of thermogravimetric analysis of gold 11-mer (Au 11 ) (Au 11 : TPP) synthesized in Reference Example 1.
  • FIG. 2 shows the results of examining the dependence of the firing time on the size of the gold cluster by diffuse reflectance spect
  • FIG. 4 shows TEM photographs and EXAFS results for samples with different firing times and carriers.
  • FIG. 5 shows TEM photographs and gold cluster sizes for samples with different firing times and carriers.
  • FIG. 6 shows an FT-IR spectrum of a sample obtained using SBA-15 (Reference Example 2) as a carrier and a firing time of 2 hours.
  • FIG. 7 shows HAADF-STEM (High-angle annular dark-field scanning transmission electromicroscopy) images and gold cluster particle size distributions at firing times of 2, 8, and 16 hours.
  • Au 11 supported on SBA-15 with a firing time of 2 hours is 0.16Au 11 -SBA (2)
  • 8 hours is 0.16Au 11 -SBA (8)
  • 16 hours is 0.16Au 11 -SBA (16). Represent each.
  • FIG. 8 shows the results of a diffuse reflection UV-vis microscope.
  • a) is 0.16Au 11 -SBA (2)
  • b) is 0.16Au 11 -SBA (8)
  • c) is 0.16Au 11 -SBA (16).
  • FIG. 9 shows the results of catalytic activity for the oxidation reaction of benzyl alcohol in Example 5.
  • A shows the relationship of log [1 / (1-X)] to the reaction time.
  • a) is 0.16Au 11 -SBA (2)
  • b) is 0.16Au 11 -SBA (8)
  • c) is 0.16Au 11 -SBA (16).
  • B shows the relationship of the normalized reaction rate constant to the diameter of the Au 11 cluster.
  • the present invention relates to a composite of gold clusters and mesoporous silica, which is composed of mesoporous silica in which gold clusters having a particle size (average particle diameter) in the range of 0.8 to 1.0 nm are supported in pores.
  • the gold clusters supported in the pores are made of gold 11-mer (Au 11 ), and the particle size of the gold 11-mer is 0.8 nm. Is not wide). Accordingly, although depending on the production conditions, the particle size (average particle diameter) of the gold cluster supported on the composite of the present invention is 0.8 nm or more and 1.0 nm or less.
  • gold clusters having a particle size exceeding 1.0 nm (individual) are also supported. However, even if it is supported, it is 30% or less. Conversely, gold clusters with particle sizes (individual) in the range of 0.8 to 1.0 nm are 70% or more of the supported gold clusters.
  • the gold cluster supported on the composite of the present invention is much finer than the gold particles supported on the composite containing gold particles described in Patent Document 1.
  • the composite of the present invention is a composite comprising a gold cluster and mesoporous silica, in other words, a gold cluster supported on mesoporous silica.
  • the particle size (average particle diameter) of the gold cluster is in the range of 0.8 to 1.0 nm.
  • a silica particle carrying a gold cluster is known, and the gold cluster has a mean particle size of 1.4 nm.
  • the pore diameter of mesoporous silica supporting gold clusters is in the range of 2 to 50 nm.
  • Mesoporous silica is porous silica having uniform and regular pores (mesopores) generally made of silicon dioxide (silica). It has pores with an almost uniform diameter called the mesopore region, ranging from 2 to 50 nm, and may have various characteristics depending on the network mode (spatial symmetry) created by the pores and the manufacturing method. It is a known group of porous materials.
  • This porous silica is one of the substances that are expected to be used as a structural member such as a separation adsorbent, a chromatography filler, a wastewater treatment agent, a catalyst, etc. due to the characteristics such as pore diameter and large surface area. It is.
  • mesopores pores with a diameter of 2 to 50 nm are defined as mesopores in the catalyst field.
  • Several methods for synthesizing mesoporous silica are known, and a sol-gel method using a surfactant as a template can be exemplified. It is known that mesoporous silica prepared using a cationic surfactant can take various types of networks (spatial symmetry) created by various pores depending on the type of the cationic surfactant (Non-patent literature). 8). In the present invention, known mesoporous silica can be used as it is.
  • various types of mesoporous silica can be used as a carrier.
  • the mesoporous silica has a pore diameter of 2 to 50 nm.
  • mesoporous silica having various pore diameters can be used depending on the type of catalytic reaction.
  • the pore diameter of mesoporous silica is preferably in the range of 2 nm or more.
  • the BET specific surface area of mesoporous silica is not particularly limited, but can be, for example, in the range of 500 to 1300 m 2 / g.
  • the BET specific surface area of mesoporous silica is preferably in the range of 600 to 1200 m 2 / g.
  • the amount of gold clusters supported in the pores of mesoporous silica is not particularly limited, but can be, for example, in the range of 0.1 to 2.5% by mass. If the amount of gold clusters supported becomes too large, the entire amount becomes difficult to be supported in the pores, so the upper limit is about 2.5% by mass. Further, if the amount of gold clusters supported is too large, the particles of gold clusters may become too large during aggregation for the production of the composite. From such a viewpoint, the supported amount of the gold cluster is preferably in the range of 0.1 to 0.5% by mass.
  • the present invention also includes a catalyst comprising the composite of the gold cluster of the present invention and mesoporous silica.
  • the composite used for the catalyst is as described above.
  • the catalyst of the present invention can be used for an oxidation reaction, for example.
  • examples thereof include oxidation reactions of primary alcohols such as benzyl alcohol and secondary alcohols such as 1-indanol.
  • the catalyst of the present invention When the catalyst of the present invention is used for an alcohol oxidation reaction, it can be carried out as follows. A composite of gold clusters and mesoporous silica is mixed and stirred with alcohol in an aqueous solution of K 2 CO 3 . This is irradiated with microwaves, and when the temperature reaches 80 ⁇ 2 ° C., hydrogen peroxide is added. However, the temperature at which hydrogen peroxide is added is not intended to be limited to 80 ⁇ 2 ° C., and may be appropriately set within a range of 50 to 90 ° C., for example, in consideration of the type of catalyst of the present invention and the type of alcohol Can do. The reaction is stopped by adding hydrochloric acid and the product is extracted with ethyl acetate. The extracted organic phase is dried over sodium sulfate and identified and quantified by gas chromatography.
  • the present invention also includes a method for producing a composite of the gold cluster and mesoporous silica of the present invention.
  • This manufacturing method is (1) A step of mixing mesoporous silica and trimeric phosphine-protected 11-mer gold clusters (hereinafter referred to as Au 11 : TTP) in a solvent to adsorb Au 11 : TTP to mesoporous silica; When (2) a step of firing at least a part of triphenylphosphine by firing Au 11 : mesoporous silica adsorbed with TTP; Is included.
  • Au 11 trimeric phosphine-protected 11-mer gold clusters
  • Au 11 : TTP an 11-mer gold cluster (hereinafter referred to as Au 11 : TTP) protected with triphenylphosphine is used.
  • the 11-mer gold cluster protected with triphenylphosphine can be synthesized from a commercially available Au (I) (TPP) Cl complex as described in Reference Example 1 described later.
  • Au 11 : TTP obtained by the method shown in Reference Example 1 contains at least one or both of [Au 11 (TPP) 8 Cl 2 ] + and Au 11 (TPP) 7 Cl 3 .
  • Au 11 : TTP can be used.
  • Mesoporous silica and Au 11 : TTP are mixed in a solvent at a predetermined ratio to adsorb Au 11 : TTP to mesoporous silica.
  • Au 11 : TTP can be mixed in the range of 0.1 to 2.5 parts by mass with respect to 100 parts by mass of mesoporous silica.
  • Au 11 : TTP is favorably adsorbed to mesoporous silica, and the degree of adsorption can be determined by the color change of the mixed solution (change from colored to colorless).
  • the solvent for example, dichloromethane, chloroform, ethanol mixture thereof and the like can be used. In particular, it is preferable to use a mixture of three solvents, dichloromethane, chloroform, and ethanol, from the viewpoint of efficiently and uniformly adsorbing Au 11 : TTP.
  • the mesoporous silica adsorbed with Au 11 : TTP is baked to remove at least a part of triphenylphosphine.
  • the firing conditions can be appropriately determined depending on the state of thermal desorption of triphenylphosphine from Au 11 : TTP. As shown in FIG. 1, in the Au 11 : TTP synthesized in Reference Example 1, triphenylphosphine is thermally desorbed at a temperature around 200 ° C. Considering this point, the firing can be performed at a temperature in the range of 180 to 220 ° C., for example.
  • the firing temperature not only affects the degree of elimination (removal) of triphenylphosphine, but also affects the particle size of the gold clusters supported in the mesoporous silica pores. As a tendency, the lower the temperature and the shorter the heating time, the smaller the gold cluster particle size. Conversely, the higher the temperature and the longer the heating time, the larger the gold cluster particle size. Considering these points, the heating temperature and time for firing are appropriately determined. However, the calcination is preferably carried out under conditions that remove substantially all of the adsorbed triphenylphosphine.
  • the heating time is in the range of 2 to 16 hours, so that substantially all of the triphenylphosphine can be removed and the particle size of the gold cluster is reduced, for example, 3 nm
  • a composite of gold clusters and mesoporous silica composed of mesoporous silica in which at least a part of gold clusters having a particle size of 3 nm or less is supported in the pores can be produced.
  • the composite of the produced gold cluster and mesoporous silica is used as it is as a catalyst.
  • the mesoporous silica having a large surface area is used as the support, the density of the adsorbed Au 11 can be suppressed. Therefore, for example, the particle size of the gold cluster can be 1 nm or less, and Au 11 is also characterized in that the size is uniform at the atomic level.
  • TTP which is an Au 11 precursor having a uniform size at the atomic level
  • an agglomeration process can be uniformly generated and the dispersibility of the gold cluster can be maintained. As a result, it can be controlled to a relatively small size.
  • Reference example 3 MCFS synthesis 1. 2 g of amphiphilic polymer P123 was added to 2M HCl solution (75 mL) and stirred at 40 ° C. for 4 hours. 2. 1 g of TMB (1,3,5-trimethylbenzene) was added and stirred at 40 ° C. for 2 hours. 3. 4.25 g of TEOS (tetraethoxysilane) was added and stirred at 40 ° C. for 24 hours. 4. Placed in an 80 ° C autoclave for 1 day. 5. Filtered and dried. 6. Baked at 500 ° C. for 6 hours in air to obtain mesoporous silica MCFS.
  • TMB 1,3,5-trimethylbenzene
  • TEOS tetraethoxysilane
  • Reference example 4 HMS synthesis method 1. Add 270 mL water to 11.5 M HCl solution (47 mL). 2. 4.74 g of CTAB (Cetyl Trimethyl Ammonium Bromide) was added and stirred at room temperature until dissolved. 3. 20.8 g of TEOS (tetraethoxysilane) was added and stirred at 40 ° C. for 24 hours. 4. Allowed to stand at room temperature for 48 hours. 5. Filter and dry. 6. Baked at 600 ° C. for 6 hours in air to obtain mesoporous silica HMS.
  • CTAB Cetyl Trimethyl Ammonium Bromide
  • Table 1 shows the BET specific surface area, total pore volume, and BJH adsorption pore diameter of the mesoporous silica synthesized in Reference Examples 2 to 4.
  • Example 1 Supporting gold on mesoporous silica 5 mg of gold 11-mer (Au 11 ) prepared in Reference Example 1 was dissolved in 24 mL of dichloromethane, and then 1 g of mesoporous silica prepared in any of Reference Examples 2 to 4 was added to this solution. Added and stirred for 2 hours. After stirring, it was filtered to obtain mesoporous silica adsorbing gold 11-mer (Au 11 ). Due to the difference in color (difference in absorption spectrum) between the solution before adsorption and the filtrate obtained after filtration, the gold 11-mer (Au 11 ) contained in the solution was adsorbed to almost 100% mesoporous silica. I understood.
  • the obtained mesoporous silica adsorbing the gold 11-mer (Au 11 ) was baked at 200 ° C. From the results of thermogravimetric analysis of gold 11-mer (Au 11 ) shown in FIG. 1, the firing temperature was set to 200 ° C.
  • FIG. 2 shows the result of examining the dependence of the firing time on the size of the gold cluster by diffuse reflectance spectroscopy when SBA-15 shown in Reference Example 2 is used as a carrier. As shown in FIG. 2, the peak of surface plasmon absorption increases with the firing time, and it can be seen that the size gradually increases.
  • FIG. 3 shows the result of examining the dependence of the carrier on the size of the material by diffuse reflectance spectroscopy.
  • FIG. 3 shows that agglomeration accompanying firing can be suppressed by using mesoporous silica as a carrier.
  • FIG. 4 shows TEM photographs and EXAFS results for samples with different firing times and carriers
  • FIG. 5 shows TEM photographs and gold particle sizes.
  • FIG. 4 shows that the gold cluster obtained by firing Au 11 : TPP adsorbed on SBA-15 for 2 hours is so small that it cannot be observed by TEM.
  • the average coordination number determined by EXAFS is 5.8 ⁇ 2.0, which corresponds to the value of face-centered cubic particles having a diameter of about 0.8 nm.
  • FIG. 6 shows an FT-IR spectrum of a sample obtained by using SBA-15 (Reference Example 2) as a carrier and a firing time of 2 hours. From FIG. 6, since the peak attributed to the organic ligand disappeared upon firing, the removal of the ligand was confirmed.
  • Example 2 When the catalytic activity for the oxidation reaction of benzyl alcohol was investigated, benzoic acid was obtained as the main product. In addition, the gold catalyst obtained showed higher activity than that of a particle size of 10 nm or more prepared by the conventional method, and the sub-nanometer size gold cluster showed the highest activity.
  • the oxidation reaction of benzyl alcohol was performed using a temperature-controlled microwave apparatus. Benzyl alcohol (31.0 mg, 0.25 mmol), K 2 CO 3 (103.7 mg, 0.75 mmol), and H 2 O (10 mL) were added to the test tube. After sonication for 2 minutes, 1% catalyst (100 mg) was added to the reaction substrate and vigorously stirred (1000 rpm). When the temperature reached 80 ⁇ 2 ° C., 0.5 ml of 30% H 2 O 2 was added. After 90 minutes, the reaction was quenched with 2 M HCl. The product was extracted 3 times with AcOEt (10 mL). The extracted organic phase was dried over Na 2 SO 4 , diluted to 100 mL, and analyzed by gas chromatography (Shimadzu, GC-2014). The results (conversion and selectivity) are shown in Table 2.
  • the catalyst of the present invention shows higher activity than the gold catalysts prepared by the conventional method (0.5Au / SBA (IP), 0.5Au / SBA (DP)), and the gold particle size decreases. It can be seen that the activity increases. Furthermore, the relative production of aldehyde (1) increased with increasing gold particle size. From the results of EXAFS shown in FIG. 4, the gold particle size is the smallest when the firing time is 2 hours and is about 0.8 nm, and when it is 8 hours, it is about 1.0 nm. Furthermore, when the firing time is 16 hours, it can be seen from the histogram shown in FIG. 5 that the gold particle size increases to 2.8 ⁇ 0.6 nm (average value and standard deviation).
  • Example 3 Examination of reusability (1) The reusability of 0.5Au 11 -SBA (2h) was investigated. After completion of the reaction, 0.5Au 11 -SBA (2h) catalyst was recovered from the reaction mixture by filtration, washed well with acetone and dried. The catalyst thus recovered was reused in the next run under the same conditions as in Example 2. The results (conversion and selectivity) are shown in Table 3.
  • Example 4 Supporting gold on mesoporous silica 4 mg (corresponding to 0.16% by mass) of the gold 11-mer (Au 11 ) (diameter 0.8 nm) prepared in Reference Example 1 was mixed with 24 mL of a mixed solvent of dichloromethane and ethanol (CH 2 Cl 2 / C 2 was dissolved in H 5 OH (80/20)), then added mesoporous silica SBA-15 of 1g prepared in reference example 2 to this solution was stirred for 2 hours. After stirring, it was filtered to obtain mesoporous silica adsorbing gold 11-mer (Au 11 ).
  • FIG. 7 shows the HAADF-STEM (High-angle annular dark-field scanning transmission electromicroscopy) images and the gold cluster particle size distribution at firing times of 2, 8, and 16 hours.
  • Au 11 supported on SBA-15 with a firing time of 2 hours is 0.16Au 11 -SBA (2)
  • 8 hours is 0.16Au 11 -SBA (8)
  • 16 hours is 0.16Au 11 -SBA (16). write.
  • the particle size of the gold cluster was evaluated by HAADF-STEM and diffuse reflectance UV-vis spectroscopy.
  • the average particle size was 0.8 ⁇ 0.3 nm at a firing time of 2 hours, 1.5 ⁇ 0.6 nm at a firing time of 8 hours, and 1.9 ⁇ 1.0 nm at a firing time of 16 hours.
  • FIG. a) is 0.16Au 11 -SBA (2)
  • b) is 0.16Au 11 -SBA (8)
  • c) is 0.16Au 11 -SBA (16).
  • the surface plasmon band of the gold cluster was not found for 0.16Au 11 -SBA (2), but it became clear as the firing time became longer. This tendency coincides with the result of HAADF-STEM.
  • Au 11 clusters aggregated into large particles by heat-induced migration.
  • 0.16Au 11 -SBA (2) the firing time was short and there was little opportunity for aggregation, and as a result, the Au 11 cluster was maintained as it was.
  • Example 5 The catalytic activity of 0.16Au 11 -SBA (2), 0.16Au 11 -SBA (8), and 0.16Au 11 -SBA (16) obtained in Example 4 for the oxidation reaction of benzyl alcohol was the same as in Example 3.
  • Table 4 shows rate constants k and k ′ in addition to the yields of benzyl alcohol (1) as a raw material and benzaldehyde (2) and benzoic acid (3) as products.
  • k is a value normalized by the surface area of the corresponding cluster on the assumption that the diameter is spherical as shown in FIG.
  • k ′ is a value normalized by a relative rate constant of 0.16Au 11 -SBA (2), and is also shown in B of FIG. k ′ indicates that the Au 11 cluster having the smallest average particle diameter (0.8 nm) has higher catalytic activity than the large Au 11 cluster (1.5 nm and 1.9 nm).
  • Example 6 Examination of reusability (2) The reusability of 0.16Au 11 -SBA (2) obtained in Example 4 was examined. After completion of the reaction, 0.16Au 11 -SBA (2) catalyst was recovered from the reaction mixture by filtration, washed well with acetone and dried. The catalyst thus recovered was reused in the next run under the same conditions as in Example 2. However, 0.5 ml of 30% H 2 O 2 was added when the temperature reached 60 ⁇ 2 ° C. The results (yield) are shown in Table 5. From the results of Table 5, it was found that, at 60 ° C., it can be repeatedly used up to 4 times without losing the catalytic activity.
  • Example 7 Oxidation of primary and secondary alcohols About 0.16Au 11 -SBA (2) obtained in Example 4, the oxidation of various primary alcohols or secondary alcohols was examined. The reaction conditions were the same as in Example 2. However, 0.5 ml of 30% H 2 O 2 was added when the temperature reached 60 ⁇ 2 ° C. The results (recovery rate and yield) are shown in Table 6.
  • the present invention is useful in the catalyst utilization field.

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Abstract

La présente invention concerne un procédé de préparation d'un agrégat d'or supporté dans la silice possédant une taille allant d'un sous-nanomètre à plusieurs nanomètres; un agrégat d'or supporté dans de la silice présentant une taille de l'ordre d'un sous-nanomètre; et un catalyseur comprenant des agrégats d'or supporté dans de la silice possédant une taille allant d'un sous-nanomètre à plusieurs nanomètres. Plus spécifiquement, la présente invention porte sur un complexe qui comprend une silice mésoporeuse et des agrégats d'or possédant une taille de particule comprise entre 0,8 et 1,0 nm et supportés dans les pores de la silice mésoporeuse; un catalyseur comprenant ledit complexe; et un procédé de production d'un complexe silice mésoporeuse/agrégats d'or, comprenant une silice mésoporeuse et des agrégats d'or possédant une taille de particule inférieure ou égale à 3 nm, et supportés dans les pores de la silice mésoporeuse. Ledit procédé de production comprend les étapes suivantes : mélange d'une silice mésoporeuse et d'agrégats d'or 11-mer protégés par triphénylphosphine (ci-dessous « Au11:TTP ») ensemble dans un solvant, afin de permettre l'adsorption de Au11:TTP sur la silice mésoporeuse; et cuisson de la silice mésoporeuse dont l'Au11:TTP a été adsorbé dessus, afin de retirer au moins une partie de la triphénylphosphine.
PCT/JP2010/055434 2009-03-26 2010-03-26 Agrégat d'or supporté dans de la silice mésoporeuse, catalyseur comprenant ledit agrégat, et procédé de production de celui-ci WO2010110447A1 (fr)

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JP2016002546A (ja) * 2014-06-16 2016-01-12 エルジー・ケム・リミテッド アリルアルコールからアクリル酸製造用不均一系触媒、これを用いたアリルアルコールからアクリル酸を製造する方法
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JP2018167998A (ja) * 2017-03-29 2018-11-01 東ソー株式会社 酸化ニオブ被覆メソポーラスシリカ及びその製造方法
CN110257054A (zh) * 2019-07-09 2019-09-20 长春工业大学 金纳米簇基荧光复合材料的制备及其在离子检测中的应用

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CN110257054A (zh) * 2019-07-09 2019-09-20 长春工业大学 金纳米簇基荧光复合材料的制备及其在离子检测中的应用

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