KR102360970B1 - Nanocatalosomes as plasmonic bilayer-shells with interlayer catalytic hot nanospaces and the manufacturing method thereof - Google Patents

Abstract

The present disclosure includes the steps of preparing a spherical porous amine silica nanoshell with an empty interior; introducing metal nanoparticle seeds to the inner and outer surfaces of the porous amine silica nanoshell by treating the porous amine silica nanoshell with a metal chloride; coating a tannic acid-Fe (TA-Fe) coordinated polymer layer on the porous amine silica nanoshell into which the metal nanoparticle seeds are introduced; and treating the metal chloride and the reducing agent to grow the metal nanoparticle seeds contained in the porous amine silica nanoshell coated with the tannic acid-Fe coordination polymer layer; It relates to a method for manufacturing a metal double-layered nano-catalosome comprising a, and to a metal double-layered nano-catalosome prepared therefrom.

Description

Nanocatalosomes having a plasmonic bilayer structure having a catalytic nanospace and a manufacturing method thereof

The present disclosure relates to a nano-catalosome having a plasmonic double layer structure having a catalyst nanospace and a method for preparing the same. Specifically, the present disclosure relates to a plasmonic double-layered nano-catalosome having a catalyst nanospace that can be used for a solar-induced reaction and a method for preparing the same.

Designing and synthesizing catalysts with complexity similar to nature on the nanoscale scale to utilize sunlight as a sustainable fuel with unprecedented functionality and versatility remains a challenge in the industry.

In addition, bilayer membrane-based hollow structures are the structures of cell endoplasmic reticulum, exosomes, carboxysomes, vacuoles, capsids and various organelles. It not only maintains key pH, ion/molecular channels and concentrations through the confined space of the polypeptide sub-nanometer (nm) formed by the activation of membrane-bound enzymes and compartmentalization substrates, but also confer biocatalytic functions.

In the synthetic domain, it can mimic the complex morphological features of natural systems on the scale of several nm, perform functionally diverse thermodynamic and industrially useful chemical reactions, and utilize sustainable natural sunlight to generate energy-intensive heat from conventional fossil fuels. It is necessary to design and synthesize a next-generation catalyst for ecological mimicry that can overcome the conditions.

Therefore, metal-based hollow structures are of great interest due to their high surface area, low density, and unique optical, chemical and compound loading properties resulting from limited quantum effects.

So far, in these miniaturized nanostructures, the inner (cavity)/outer surface or intershell gaps can be tens or without control over the randomly occurring number/subnano-sized pores within the shell or intershell region. It could only be manipulated on the scale of several hundred nanometers. However, this size has limitations in developing physicochemical and catalytic properties according to the structure, and so far, it has been difficult to achieve controllable structural complexity on the scale of several nm while having a limited cavity for high-efficiency plasmon-induced catalysis in a single structure. and there is a need for research on it.

The present disclosure seeks to provide a customizable and versatile catalytic nanoreactor with a new kind of controllable double layer space.

An object of the present disclosure is to provide a nano catalosome exhibiting high catalytic performance.

An object of the present disclosure is to provide a next-generation metal bilayer-based nanoreactor.

The present disclosure aims to provide a nano-catalosome capable of complex structural and functional manipulations on the scale of several nm.

The metal double-layered nano-catalosome of one embodiment of the present disclosure is a metal composed of a spherical porous amine silica nanoshell with an empty interior and a plurality of metal nanoparticles uniformly present on the inner surface and the outer surface of the porous amine silica nanoshell It may include a double layer.

The plurality of metal nanoparticles may include at least one selected from the group consisting of gold (Au), platinum (Pt), and palladium (Pd).

The plurality of metal nanoparticles may be coated with platinum (Pt), palladium (Pd), or a combination thereof on gold (Au) nanoparticles.

The metal double layer may include a plurality of nano-sized pores defined by the metal nanoparticles constituting the outer metal layer and the metal nanoparticles constituting the inner metal layer.

The size of the pores may be determined by the size of the metal nanoparticles constituting the outer metal layer of the metal double layer and the metal nanoparticles forming the inner metal layer.

The nano-sized pores defined by the metal nanoparticles constituting the outer metal layer and the inner metal layer may have a size of 6 nm or less.

The plurality of pupils may provide a plasmonic coupling effect and coupling electromagnetic hotspot.

A catalytic reaction may occur in the plurality of cavities.

The thickness of the outer shell of the metal double layer may be 15 nm or less, and the thickness of the inner shell may be 12 nm or less.

A method for preparing a metal double-layered nano-catalosome according to an embodiment of the present disclosure includes the steps of preparing a spherical porous amine silica nanoshell with an empty interior; introducing metal nanoparticle seeds to the inner and outer surfaces of the porous amine silica nanoshell by treating the porous amine silica nanoshell with a metal chloride; coating a tannic acid-Fe (TA-Fe) coordinated polymer layer on the porous amine silica nanoshell into which the metal nanoparticle seeds are introduced; and treating the metal chloride and the reducing agent to grow the metal nanoparticle seeds included in the porous amine silica nanoshell coated with the tannic acid-Fe coordination polymer layer.

Growing the metal nanoparticle seeds; may be a step of controlling the thickness of the metal double layer by adjusting the amount of the metal chloride used.

Growing the metal nanoparticle seeds; in the case of using 3 mg of porous amine silica nanoshell having a diameter of 75±3 nm, may be a step of growing by adding a metal chloride having a concentration of 5 mM to 1.0 ml or less.

Growing the metal nanoparticle seed;

In the case of using 3 mg of porous amine silica nanoshell having a diameter of 75 ± 3 nm, it may be a step of growing by adding a reducing agent having a concentration of 50 mM to 1.0 ml or less.

In the method for manufacturing a nano-catalosome in the form of a metal double layer, the metal nanoparticles may be at least one selected from the group consisting of gold (Au), platinum (Pt), and palladium (Pd) nanoparticles.

The step of coating a tannic acid-Fe (TA-Fe) coordinated polymer layer on the porous amine silica nanoshell into which the metal nanoparticle seed is introduced; is an aqueous solution by dispersing the porous amine silica nanoshell introduced with the metal nanoparticle seed in distilled water. to prepare; adjusting the pH of the aqueous solution to 8 to 12; And it may be a step of mixing tannic acid and iron (III) chloride in the pH-controlled aqueous solution.

The step of growing the metal nanoparticle seed; dispersing the porous amine silica nanoshell introduced with the metal nanoparticle seed coated with a tannic acid-Fe (TA-Fe) coordination polymer layer in a PVP aqueous solution; and continuously adding a metal chloride and a reducing agent to grow the metal nanoparticle seeds.

The step of growing the metal nanoparticle seeds; the tannic acid-Fe (TA-Fe) coordinated polymer layer is decomposed, and then metal ions are attached to the plurality of metal nanoparticle seeds disposed inside and outside the porous silica nanoshell to form a metal Nanoparticle seeds may be growing.

In the step of introducing the metal nanoparticle seed, the metal chloride may be at least one selected from the group consisting of HAuCL ₄ , Na ₂ PdCl ₄ and Na ₂ PtCl ₄ .

In the step of growing the metal nanoparticle seeds, the metal chloride may be at least one selected from the group consisting of HAuCL ₄ , Na ₂ PdCl ₄ and Na ₂ PtCl ₄ .

In the step of growing the metal nanoparticle seed, the reducing agent may be hydroquinone.

According to one embodiment of the present disclosure, it is possible to provide a nano catalosome, which is a metal bilayer-based hollow nanostructure that mimics a bilayer membrane-based vesicle structure preferred in nature.

According to one embodiment of the present disclosure, it is possible to provide a nano-catalosome having a unique double-layer structure and high catalytic performance.

The nano-catalosome of an embodiment of the present disclosure and a method for manufacturing the same may provide a next-generation metal double-layer-based nano-reactor,

According to one embodiment of the present disclosure, it is possible to provide a nano-catalosome capable of complex structural and functional manipulation on a scale of several nm.

By expanding the usefulness of solar energy through the nano-catalosome of one embodiment of the present disclosure, it is possible to enable the sustainable development of high-functional catalytic chemistry.

1 shows the synthesis mechanism of a nano-catalosome and its application. FIG. 1 a shows a method for synthesizing a metal double-layer nano-catalosome having a cavity (cavity), and shows the change in the interlayer pore structure according to the size of metal nanoparticles, and FIG. 1 b is a nano-catalosome. A schematic diagram of the solar-induced reaction is shown.
Figure 2 shows the nano-catalosomes of different structures. FIG. 2 a shows TEM images of (i) Au-4-NCat, (ii) Pt-NCat, and (iii) Pd-NCat. Figure 2b shows (i)TEM image, (ii) HRTEM image, (iii)STEM, STEM-EDS component analysis and (iv) EDS component line profile of Pt/Au-4-NCat. FIG. 2 c shows (i)TEM image, (ii)HRTEM image, and (iii)STEM, STEM-EDS component analysis of Pt/Au-4-Ncat.
Figure 3 confirms the plasmonic properties according to the structure of the nano-catalosome, a is a TEM image of Pt/Au-1~4-NCat synthesized as the amount of metal precursor is increased (i-iv, from left to right) , b is a UV-vis spectrum of Pt/Au-1 to 4-NCat, and c is a representative SERS spectrum of 4-aminothiophenol (4-ATP)-modified Pt/Au-1 to 4-NCat (i ), and the average CS(ii), CC(iii) Raman peak signal of the values recorded at 10 points within each sample, and d is the Raman temperature measurement experimental result of 4-ATP-modified Pt/Au-1~4 -SERS Stoke peak intensity (IS) and anti-Stoke peak intensity (IAS) of the CS peak of -NCat (i) and the Boltzmann distribution recorded at 10 points within each sample, IS and of each vibrational state given by IAS Corresponding temperatures (ii) estimated from populations are shown.
Figure 4 confirms the catalytic performance of the nano-catalosome in the receptor-free dehydrogenation reaction (AD), a is a performance comparison table with Pt / Au-4-NCat and previously reported catalysts. b is a schematic diagram of [Pt]-catalyzed dehydrogenation reaction of THQ and the conversion rate according to time when using Pt/Au-1 to 4-NCat, c is Pt/ When Au-4-NCat was used, the conversion rate with time was shown, d is the conversion number of THQ dehydrogenation (TOF(h ^-1 )) when using various catalysts, and e is Pt according to the substrate It shows TOF(h ^-1 ) and product yield of dehydrogenation using /Au-4-NCat, and error bars in b, d and e show the standard deviation of three replicates.
5 is a Suzuki-Miyaura cross-linking reaction confirming the catalytic performance of the nano-catalosome, a is a [Pd]-catalytic coupling reaction of aryl boronic acid and aryl halide, b is Pd/Au-1 to 4- It shows the conversion rate with time of iodobenzene and phenyl boronic acid using NCat, c is the TOF (s ^-1 ) graph of the cross-linking reaction of iodinebenzene and phenyl boronic acid using different catalysts, and d is the substrate The TOF(s ⁻¹ ) of the Suzuki-Miyaura cross-linking reaction using Pd/Au-4-NCat according to B and c error bars represents the standard deviation of three replicates.
Figure 6 is to confirm the catalytic performance of the nano-catalosome in the alkyne cyclization reaction, a is a [Au] catalytic alkyne cyclization reaction schematic diagram of different phenol esters of phenyl propanoic acid, b is Au-1 ~ 4-NCat It shows the conversion rate of the alkyne cyclization reaction according to the time used, c shows the conversion rate of the alkyne cyclization reaction using Au-4-NCat according to the substrate, and the error bar in b is the standard deviation of three repeated experiments. is shown.
7 is a TEM image of the AuNC@h-SiO ₂ synthesis process, a is h-SiO ₂ , b is h-SiO ₂ treated with HAuCl ₄ , c is NaBH ₄ continuously treated therewith , d shows AuNC@h-SiO ₂ on which TA-Fe coating is completed.
8 shows TEM images of Au-1-NCat to Au-3-NCat.
9 shows a. ascorbic acid, b. sodium citrate, c. A TEM image of sodium borohydride and d. hydroxylamine as a reducing agent is shown.
10 is a, b shows XPS peaks of Pt/Au-4-NCat, c, d is Pd/Au-4-Ncat, and e is Au-4-Ncat.
11 shows the analysis data of Pd/Au-1 to 4-NCat, a to c are TEM images of Pd/Au-1-Ncat to Pd/Au-3-Ncat, and d is Pd/Au-4 STEM-HDAAF and EDS-component line profiles of -NCat are shown.
12 is a graph showing the photothermal properties of the nano-catalosome, a is Pt/Au-1-NCat to Pt/Au-4-NCat, b is the result of varying the concentration of the nano-catalosome, c is The results of Pd/Au-4-NCat, Pt/Au-4-NCat, and Au-4-NCat at the same concentration are shown.
13 shows a TEM image of s-Pt/Au-NCat.
14 shows the number 5 The TEM image of Pt/Au-4-NCat after dehydrogenation reuse is shown.
15 shows the catalyst regeneration test results of Pt/Au-4-NCat and Pt-AuNR.

The terms first, second and third etc. are used to describe, but are not limited to, various parts, components, regions, layers and/or sections. These terms are used only to distinguish one part, component, region, layer or section from another part, component, region, layer or section. Accordingly, a first part, component, region, layer or section described below may be referred to as a second part, component, region, layer or section without departing from the scope of the present invention.

The terminology used herein is for the purpose of referring to specific embodiments only, and is not intended to limit the present invention. As used herein, the singular forms also include the plural forms unless the phrases clearly indicate the opposite. The meaning of "comprising," as used herein, specifies a particular characteristic, region, integer, step, operation, element and/or component, and includes the presence or absence of another characteristic, region, integer, step, operation, element and/or component. It does not exclude additions.

When a part is referred to as being “on” or “on” another part, it may be directly on or on the other part, or the other part may be involved in between. In contrast, when a part is referred to as being "directly above" another part, the other part is not interposed therebetween.

In addition, unless otherwise specified, % means weight %, and 1 ppm is 0.0001 weight %.

Although not defined otherwise, all terms including technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention belongs. Commonly used terms defined in the dictionary are additionally interpreted as having a meaning consistent with the related technical literature and the presently disclosed content, and unless defined, are not interpreted in an ideal or very formal meaning.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily implement them. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.

Plasmonic metal-based nanostructures composed of controllable narrow gaps, junctions, and cavities of a few nm dramatically increase wide optical quenching through collective excitation and extensive multimode plasmonic coupling, and electromagnetic fields to higher levels than isolated nanoparticle (NP) devices. can create This nanoscale effect results in efficient generation of charge carriers and localized increase in photothermal temperature, which is very beneficial for promoting interfacial catalysis.

Accordingly, in the present disclosure, it is an object of the present disclosure to provide a plasmon-catalyzed nanoreactor having a structure similar to that of a natural biomimetic double-layered endoplasmic reticulum (NCat). Nanocatalosomes are hollow shell-in-shell structures of a metal bilayer composed of an array of closely-gapped nanoparticle units, which can create a few nm interlayer catalytic space for organic reactions (Fig. 1). The interlayer space of a few nm of the nano-catalosome may include a plurality of plasmonic nano-cavities (several nm in size, for example, 0.5 to 6 nm in diameter) closely connected to and controllable with catalytic noble metals (Au, Pt, Pd). In the bilayer structure of nanocatalosomes, inter-shell-confined plasmon-coupled hot-nanospaces inside a few nm cavities may play a central role in synergistic catalytic effects to achieve a variety of major organic transformation reactions. This is a quantitative transformation superior to recent gold nanorod-based plasmon-catalysts by acceptorless dehydrogenation, Suzuki-Miayura cross-coupling, and alkynyl-annulation reactions. , the number of turns (Turnover frequency, TOF) may be provided.

Through the present disclosure, it is possible to prepare a framework for a functional and customizable next-generation nanoreactor that can efficiently perform various chemical transformations using eco-friendly solar energy.

In various plasmon-catalyzed nanocatalosomes, a bilayer shell with a large number of nanogaps/cavities with a size of several nm imparts a controllable plasmonic binding effect, and by efficiently utilizing a wide range of sunlight, local photothermal heating and It is a major structural feature that drives the generation of plasmonic charge carriers.

By implementing a suitably customized nano-catalosome, under weak sunlight irradiation, the N-hetero cycle at an unprecedented rate of conversion (TOF) (h-1) up to 11 times higher than that of conventional Pt-AuNR plasmonic catalysts. Receptor-free dehydration can be achieved. On the other hand, when this reaction is carried out using an existing catalyst, a very long time (>24 hours) and high temperature thermal conditions (up to 150 °C) are required.

Through various functional customizations, nano catalosomes performed industrially important Suzuki-Miyauri CC cross-linking (TOF) 18 s ⁻¹ or less) and alkyne cyclization reactions, resulting in the highest conversion number (TOF) recorded so far. An excellent yield can be exhibited with the highest value.

These various active nano-catalosomes can show significantly higher catalytic performance than the reported nanoparticle (NP)-based catalysts due to their unique bilayer structure.

Hereinafter, each step will be described in detail.

The present disclosure is a metal bilayer nano-catalosome, a metal bilayer comprising a spherical porous amine silica nanoshell with an empty interior and a plurality of metal nanoparticles uniformly present on the inner and outer surfaces of the porous amine silica nanoshell may include

The plurality of metal nanoparticles may include at least one selected from the group consisting of gold (Au), platinum (Pt), and palladium (Pd).

The plurality of metal nanoparticles may be coated with platinum (Pt), palladium (Pd), or a combination thereof on gold (Au) nanoparticles.

The metal double layer may include a plurality of nano-sized pores defined by the metal nanoparticles constituting the outer metal layer and the metal nanoparticles constituting the inner metal layer. That is, cavities may be included between the outer metal layer and the inner metal layer of the metal double layer, and there are a plurality of cavities along the metal double layer.

The size of the pores may be determined by the size of the metal nanoparticles constituting the outer metal layer of the metal double layer and the metal nanoparticles forming the inner metal layer.

Specifically, as the size of the metal nanoparticles constituting the outer metal layer of the metal double layer and the metal nanoparticles constituting the inner metal layer increases, the size of the pores may decrease. Conversely, as the size of the metal nanoparticles decreases, the size of the pores may increase. Here, the size of the metal nanoparticles may be determined by the amount of metal chloride treated during the metal nanoseed growth process in the method for manufacturing a metal double-layered nano-catalosome.

The nano-sized pores defined by the metal nanoparticles constituting the outer metal layer and the inner metal layer may have a size of 6 nm or less. Specifically, the nano-sized pores may have a size of 0.1 to 6 nm, more specifically 0.5 to 6 nm, or 0.5 to 2 nm, or 1 to 2 nm. As will be described below, nano-sized pores have plasmonic properties and can impart a catalytic effect, which is determined by how closely the pores are small and arranged.

The plurality of pupils may provide a plasmonic coupling effect and coupling electromagnetic hotspot. Specifically, the smaller the size of the plurality of pupils, the better the plasmon coupling effect and the coupling electromagnetic hotspot can be provided. In addition, the effect of the plasmon coupling effect and the coupling electromagnetic hot spot may be different depending on the size of the cavity and may not be affected by the type of metal constituting the metal nanoparticles.

A catalytic reaction may occur in the plurality of cavities.

The thickness of the outer shell of the metal double layer may be 15 nm or less, and the thickness of the inner shell may be 12 nm or less. Specifically, the thickness of the outer shell may be 1 to 15 nm, and the thickness of the inner shell may be 1 to 12 nm.

A method for preparing a nano-catalosome in the form of a metal double layer according to an embodiment of the present disclosure includes the steps of preparing a spherical porous amine silica nanoshell with an empty interior; introducing metal nanoparticle seeds to the inner and outer surfaces of the porous amine silica nanoshell by treating the porous amine silica nanoshell with a metal chloride; coating a tannic acid-Fe (TA-Fe) coordinated polymer layer on the porous amine silica nanoshell into which the metal nanoparticle seeds are introduced; and treating the metal chloride and the reducing agent to grow the metal nanoparticle seeds contained in the porous amine silica nanoshell coated with the tannic acid-Fe coordination polymer layer; may include

The step of growing the metal nanoparticle seed may be a step of controlling the thickness of the metal double layer by controlling the amounts of the metal chloride and the reducing agent used. Specifically, if the amount of metal chloride added in the step of growing the metal nanoparticle seed is increased, the metal nanoparticle may grow significantly and the thickness of the metal bilayer may be increased.

Specifically, the step of growing the metal nanoparticle seeds; in the case of using 3 mg of a porous amine silica nanoshell having a diameter of 75 ± 3 nm, may be a step of growing by adding a metal chloride having a concentration of 5 mM to 1 ml or less. Specifically, 5 mM of the metal chloride may be 0.1 to 1 ml, more specifically 0.38 to 0.9 ml, more specifically 0.6 to 0.9 ml, and more specifically 0.75 to 0.9 ml. As the amount of metal chloride processed increases, the metal nanoseeds located in the outer shell and the inner shell grow significantly, and the size of the cavity, which is a catalytic reaction site, becomes smaller, thereby providing a desirable nano-catalosome.

Specifically, the step of growing the metal nanoparticle seeds; in the case of using 3 mg of a porous amine silica nanoshell having a diameter of 75±3 nm, may be a step of growing by adding a reducing agent having a concentration of 50 mM to 1 ml or less. Specifically, the reducing agent having a concentration of 50 mM may be 0.1 to 1 ml, more specifically 0.38 to 0.9 ml, more specifically 0.6 to 0.9 ml, and more specifically 0.75 to 0.9 ml.

More specifically, the step of growing the metal nanoparticle seed; is grown by adding a metal chloride in an amount so that the metal nanoparticle per 1mg of the porous amine silica nanoshell having a diameter of 75±3nm is 2.0*10 ^-6 mol or less. It may be a step to

Specifically, the amount of metal nanoparticles per 1 mg of porous amine silica nanoshell is 0.05*10 ^-6 to 2.0*10 ^-6 mol, more specifically 0.063*10 ^-6 to 2.0*10 ^-6 mol, 0.063*10 ^-6 to 1.5* 10 ^-6 mol, 1.0*10 ^-6 to 1.5*10 ^-6 mol, or 1.25*10 ^-6 to 1.5*10 ^-6 mol.

Specifically, the step of growing the metal nanoparticle seed may be a step of adding a reducing agent in an amount 10 times the amount of the added metal chloride.

In the method for manufacturing a nano-catalosome in the form of a metal double layer, the metal nanoparticles may be at least one selected from the group consisting of gold (Au), platinum (Pt), and palladium (Pd) nanoparticles. Specifically, the metal nanoparticles may further include platinum (Pt), palladium (Pd), or a combination thereof in gold (Au) nanoparticles.

The step of coating a tannic acid-Fe (TA-Fe) coordinated polymer layer on the porous amine silica nanoshell into which the metal nanoparticle seed is introduced; is an aqueous solution by dispersing the porous amine silica nanoshell introduced with the metal nanoparticle seed in distilled water. to prepare; adjusting the pH of the aqueous solution to 8 to 12; And it may be a step of mixing tannic acid and iron (III) chloride in the pH-controlled aqueous solution. Specifically, the pH of the aqueous solution may be 10.

The step of growing the metal nanoparticle seed; dispersing the porous amine silica nanoshell introduced with the metal nanoparticle seed coated with a tannic acid-Fe (TA-Fe) coordination polymer layer in a PVP aqueous solution; and continuously adding a metal chloride and a reducing agent to grow the metal nanoparticle seeds.

The step of growing the metal nanoparticle seeds; the tannic acid-Fe (TA-Fe) coordinated polymer layer is decomposed, and then metal ions are attached to the plurality of metal nanoparticle seeds disposed inside and outside the porous silica nanoshell to form a metal Nanoparticle seeds may be growing.

In the step of introducing the metal nanoparticle seed, the metal chloride may be at least one selected from the group consisting of HAuCL ₄ , Na ₂ PdCl ₄ and Na ₂ PtCl ₄ .

In the step of growing the metal nanoparticle seeds, the metal chloride may be at least one selected from the group consisting of HAuCL ₄ , Na ₂ PdCl ₄ and Na ₂ PtCl ₄ .

In the step of growing the metal nanoparticle seed, the reducing agent may be hydroquinone. When another reducing agent is substituted for the hydroquinone, the metal double layer structure may not be formed.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily implement them. However, the present invention may be embodied in various different forms, and is not limited to the embodiments described herein.

(Synthesis of Nano Catalosomes)

A thin film chemical reaction consisting of particles (AuNC@h-SiO ₂ ), and TA-Fe (tannic acid-Fe) coordinated polymers with Au-seed introduced into the hollow porous amine silica nanoshell (h-SiO ₂ ) It was attempted to synthesize a nano-catalosome using the modification (FIG. 7). 7 is a TEM observation of the synthesis process of AuNC@h-SiO ₂ , and shows the TA-Fe coating process after continuous treatment with HAuCl ₄ and NaBH ₄ on a porous amine silica nanoshell (h-SiO ₂ ). have.

Thus, a mixture of h-SiO ₂ (0.3ml, 10mg/ml) and HAuCl ₄ (1ml, 15mM) having a diameter of 75±3nm was vortexed at 25° C. for 2 hours (vortex, 1000 rpm) to form h-SiO ₂ Gold (Au) nanoparticles seeds were introduced on the inner and outer surfaces. After washing the excess HAuCl ₄ with distilled water (1ml, 2 times), NaBH ₄ aqueous solution (0.2ml, 100 mM) was quickly added to centrifuge and wash the brown solution of AuNC@h-SiO ₂ (1ml, 2 times), and dispersed in distilled water for further use. To synthesize PtNC@h-SiO ₂ and PdNC@h-SiO ₂ , HAuCL ₄ was replaced with Na ₂ PdCl ₄ and Na ₂ PtCl ₄ , respectively, and the same process was performed.

In the next step an aqueous solution of MNC@h-SiO ₂ (M=Au, Pt, Pd) at pH 10 (adjusted with 1M NaOH) with tannic acid (0.06 ml, 10 mM) and iron(III) chloride (0.06 ml, 10 mM) After mixing with and vigorously vortexing at 25 °C for 30 seconds, MNC@h-SiO ₂ Tannic acid-Fe(TA-Fe) coordination-polymer layer was coated on the surface. The resulting particles were centrifuged and washed with distilled water (1 ml, twice), and then dispersed in distilled water.

In the final step, when M is Au, AuNC@h-SiO ₂ coated with TA-Fe from the previous step for the synthesis of Au-4-Ncat, which is a nano-catalosome of an Au-double-layer structure, was mixed with a PVP aqueous solution (2% , 0.6ml) and then HAuCl ₄ (0.9ml, 5mM) and hydroquinone (0.9ml, 50mM) were successively added. This allows Au-seeds to be uniformly and large to grow densely AuNP (gold nanoparticles) units on the outer and inner surfaces of the h-SiO ₂ template, resulting in Au- double-layered nano-catalosomes can be formed (FIG. 2). a and Fig. 8). Then, the reaction mixture was vortexed at 25° C. for 30 minutes and then washed with distilled water (1 ml, twice) to obtain red-blue Au-4-NCat.

For the synthesis of Au-1-NCat, Au-2-NCat, and Au-3-NCat, 0.38, 0.6, and 0.75 ml of HAuCl ₄ (5 mM) and hydroquinone (50 mM) were used, respectively. In Au-1-NCat to Au-4-NCat, 1 to 4 are numbered according to the amount of gold attached to the nano-catalosome, where 1 indicates the smallest amount of gold and 4 indicates the largest amount of gold. it means.

Au nanoparticle growth mechanism, TA-Fe nanofilm is decomposed in the presence of HAuCl ₄ by Fe(III)-TA coordination chemistry according to pH, AuNC@h-SiO ₂ TA having many free catecholic moieties on the surface of -forms oligomers This is followed by penetration of Au ³⁺ towards Au-seeds through the porous amino silica layer (Fig. 1a). When hydroquinone is replaced with another reducing agent, the desired Au bilayer structure is not obtained. Referring to Figure 9, instead of hydroquinone a. ascorbic acid, b. sodium citrate, c. When sodium borohydride and d. hydroxylamine were used as reducing agents, it was confirmed that a double-layer structure was not obtained.

This strategy was also applied to synthesize the bilayer structure of each other noble metal such as Pt and Pd (Pd-NCat and Pd-NCat) by replacing HAuCl ₄ with Na ₂ PtCl ₄ and Na ₂ PdCl ₄ , respectively (Fig. 2). b, c). TA-oligomers do not remain in the final product, Au-1 to 4-NCat, as they are washed in distilled water after the formation of Au-double-layered nano-catalosomes.

That is, when the seed is grown with HAuCl ₄ as it is on AuNC@h-SiO ₂ , Au-NCat is grown, and when grown with Na ₂ PtCl ₄ , Pt/Au-NCat is grown, and when grown with Na ₂ PdCl ₄ , Pd/Au-NCat is grown. Au-NCat can be grown.

As shown in the transmission electron microscopy (TEM) image of the prepared Au-4-NCat (FIG. 2a), the outer Au layer grew slightly thicker (14 ± 1 nm) than the inner Au layer (11 ± 1 nm) and was densely arranged It is in the form of a hollow metal bilayer composed of fused Au units. And the interlayer space includes a plurality of cavities (cavities) with a size of several nm defined by AuNPs, which can be accessed externally through narrow interparticle channels between non-agglomerated AuNP units in the outer Au layer. In this experimental example, it was found that Au-4-NCat had pupils of 0.5 to 6 nm in diameter. The pupil 6 nm is the largest, and there were generally many pores within 0.5 to 2 nm, which are advantageous for exhibiting catalytic activity.

The prepared Au-1-NCat to Au-3-NCat do not clearly show the boundary between the outer and inner Au layers compared to Au-4-NCat as shown in FIG. 8 showing its TEM image.

The manufacturing method of the present disclosure can finely control the size and spatial configuration of the plasmonic (Au) component according to the amount of the metal precursor used to prepare the nano-catalosome. For example, the use of small amounts of HAuCl ₄ results in larger inter-particle separation and smaller AuNPs with larger spaces between the inner and outer layers. As a larger amount of Au ³⁺ is used, the thickness of the outer and inner layers gradually increases (a in FIG. 3 for Pt/Au-1 to 4-NCat, a diagram for Pd/Au-1 to 4-NCat) 2 c and FIG. 11 , estimated as Pt/Pd: Au = 20:80 by ICP). That is, the thickness of the outer and inner Au layers, the interparticle distance between AuNP units, and thereby the size and geometry of the interlayer nanocavities can be finely tuned. These structural modifications can tune and optimize the plasmonic coupling and structure of the 'hotspots', which have a significant impact on the optical, thermal plasmonic and catalytic properties of different structures.

In addition, after reducing Pt and Pd precursors, Na ₂ PtCl ₄ (5mM) and Na ₂ PdCl ₄ (5mM) with ethylene glycol at 70°C, Pt and Pd can be deposited on the plasmonic double layer structure of Au-4-NCat. have. Thereby, it can be functionalized with various catalytic metals (Pt and Pd) to provide a bilayer structure of two metals, namely Pt/Au-4-NCat and Pd/Au-4-NCat. Specifically, for M/Au-4-NCat (M=pt, Pd) synthesis, a solution of Au-4-NCat was mixed with Na ₂ PtCl ₄ /Na ₂ PdCl ₄ (0.2ml, in 5mM H ₂ O) and ethylene It was mixed with glycol (0.5 ml) and the reaction mixture was vortexed at 70° C. for 15 minutes, and the resulting NPs were washed with distilled water (1 ml, twice). The prepared M/Au-4-Ncat was analyzed by HAADF-STEM, EDS elemental mapping, line-profiling, and X-ray photoelectron spectroscopy (XPS) (Fig. 2 b, c, Fig. 10, and Fig. 11). It could be confirmed that Pt/Pd metal was coated on the plasmonic AuNP units of both the outer and inner layers. In addition, it was confirmed that the inter-particle nanogap between the adjacent AuNP units and the intershell nanospace was constantly maintained. In particular, it was confirmed that numerous 3D nanocaves were formed in the pupil shell-in-shell arrangement.

(plasmonic properties of nano-catalosomes)

As shown in Fig. 3b, as the size of AuNP units in different Pt/Au-1~4-NCat structures gradually increased, the light absorption rate was improved and the UV-vis spectrum from visible to near-infrared region was significantly expanded. This was observed. This is because of the plasmon coupling effect that occurs when the nano-gap between the AuNP units becomes very narrow (below 1 nm) when the limited cavities are extensively formed in the intershell nanospace.

In addition, Pt/Au-1~4-NCat showed high efficiency in photothermal conversion using sunlight (300 W Xe lamp, 1W/cm ² ), and can control photothermal temperature well through various NCat structures and concentrations. there was. In the case of Pt/Au-4-NCat, the highest temperature rise (up to 90° C.) was shown between the structures of Pt/Au-1 to 4-NCat within 6 minutes of light exposure and at an NP concentration of 0.5 mg/ml ( FIG. 12 ). of a). On the other hand, by lowering the NP concentration to 0.05 mg/ml at the same amount of light, it was possible to maintain the solution temperature close to room temperature (up to 28° C.) ( FIG. 12 b ).

In particular, the photothermal effect did not show a significant difference between Pt/Au-4-NCat, Pd/Au-4-NCat and Au-4-NCat (FIG. 12 c), which is a catalytic component (Pt in thermal plasmonic properties). /Pd) is very small.

To verify the existence of electromagnetic hotspots, the surface intensity and surface-enhanced Raman Scattering (SERS) spectra of 4-aminothiophenol (4-ATP, Raman reporter) in Au-1~4-NCat were measured. As can be seen from c of FIG. 3 , the SERS signal intensity at 1072 cm ⁻¹ (CS stretching) and 1572 cm ⁻¹ (CC stretching) was higher in the case of Au-4-NCat compared to other Au-1 to 3-NCat. increased dramatically (about 34 times that of AuNC@h-SiO ₂ ). Here, the narrowest plasmonic nanocavities are formed in the bilayer, creating the maximum number of highly coupled electromagnetic hotspots.

In addition, to estimate accurate photothermal local temperatures in different Au-1 to 4-NCat, the previously reported Raman thermometry was used, which is proportional to the number of vibrational states with temperature in the Boltzmann distribution, Stokes and anti-Stokes. Based on SERS peak intensity (details specified in SI). The local temperature of Au-4-NCat is estimated to be about 180 °C (Fig. 3d).

Hereinafter, various NCat with controllable structure, composition, and optical/plasmonic properties were synthesized, and after establishing the presence of high-coupled electromagnetic and hotspots in the bilayer structure, tests for their catalytic applicability were performed.

(Dehydrogenation of THQs and derivatives using Pt/Au-nano catalosomes)

Acceptorless dehydrogenation (AD) of the N-hetero cycle under sunlight as the only energy source without other additives was tested using Pt/Au-1~4-NCat ( FIG. 4 ). Dehydrogenation is an important step in the synthesis of numerous pharmaceutical and bioactive heterocyclic scaffolds of great value to promote organic hydrides as hydrogen storage materials for commercial fuel cells.

In the case of the conventional two-step highly endothermic dehydrogenation reaction of the N-hetero cycle, a non-recyclable and air-sensitive metal-based homogeneous catalyst, harsh high-temperature conditions (over 135°C), long reaction time (>24 hours), and additional oxidizing agents, bases and a heterogeneous catalyst that requires a hydrogen acceptor, very difficult synthesis conditions, toxic ammonia flow, a narrow light absorption profile, and a very small number of photocatalysts that require a long reaction time compared to a high catalyst amount (FIG. 4a).

Accordingly, 1,2,3,4- as a substrate to investigate the AD catalyst reaction in the presence of Pt/Au-1~4-NCat (0.5 mol% Pt) and sunlight (300W Xe lamp, 0.7 W/cm ² ) It was decided to convert tetrahydroquinoline (THQ).

Dissolve THQ (1,2,3,4-tetrahydroquinoline, 0.11 mmol) and Pt/Au-1 to 4-Ncat ([Pt] = 0.50 mol%) in DMSO-d6 (3.0 ml) in a quartz reaction cell made it Under the condition of bulk temperature control (about 25 ℃) and dark environment/light irradiation (300 W Xe lamp with 510 mM pass filter, power density of incident light is 0.7 Wcm ^-2 ) excluding the thermal effect of irradiated light by the circulation cooling system The reaction proceeded.

The reaction was monitored by measuring the time-lapse yield of the product quinoline through 1H NMR (FIG. 4b). When using Pt/Au-4-NCat, the product quinoline started to form within 5 minutes and reached a yield >99% within 30 minutes at a bulk reaction temperature of 25 °C (TOFPt = 430h ^-1 ). The temperature of the bulk reaction solution did not rise significantly due to the highly localized photothermal effect in the confined bilayer structure of NCat. On the other hand, in the absence of sunlight, quinoline was not formed even after 2 hours. Under the same reaction conditions, Pt/Au-1~3-NCat with small interlayer cavities and wide plasmon gap showed much slower reaction, providing yields of 10%, 17%, and 48%, respectively, so that the structure of NCat affects the catalytic performance. It was found to have a major effect (Fig. 4d).

When a single reaction using Pt/Au-4-NCat was monitored in the order of on/off of the light source over time, it was observed that THQ was smoothly transformed into quinoline in the sunlight irradiation section (Fig. 4c), The transformation stopped when the light source was turned off. This result means that the reaction can only proceed with continuous plasmonic excitation.

To distinguish the effect of the plasmonic component of Pt/Au-4-NCat on the catalytic effect, Pt-NCat (Pt bilayer without Au component) was tested for the dehydrogenation of THQ under sunlight with a yield of less than 5% (TOFPt). < 10 h ^-1 ) was confirmed (FIG. 4 d). This means that the plasmonic component plays an important role in the high catalytic performance of Pt/Au-4-NCat.

To further verify the effect of the metal bilayer structure and the resulting interlayer plasmon-catalyzed nanopores, we synthesized a nanocatalyst with only a single shell composed of Pt-modified AuNP units on silica nanoparticles (Fig. 13). This is a nanostructure structurally very similar to Pt/Au-4-NCat except that there is no inner AuPt layer, and in the present disclosure, it will be named as s-Pt/Au-NCat. This s-Pt/Au-NCat had a yield of 25% from THQ to quinoline (TOF = 65 h ⁻¹ ), which was much inferior to Pt/Au-4-NCat having a bilayer structure (Fig. 4d). ).

In particular, the TOF (h ^-1 ) of Pt/Au-4-NCat was found to be up to 11 times higher than that of Pt-AuNR (Pt-Au nanorods), which is the latest among existing plasmonic catalysts under the same reaction conditions. This indicates that the plasmonic catalyst structure confined to the bilayer of NCat has great advantages over isolated plasmonic NP-based catalysts.

In addition, compared to the previously reported photocatalytic h-BCN for the dehydrogenation reaction (83% conversion in 12 h using 10 mg of catalyst for 0.3 mmol of substrate), Pt/Au-4-NCat was significantly faster A reaction was shown (>99% conversion, reaction for 30 min using 0.5 mol % [Pt] to 0.11 mmol substrate). In addition, solar-activated Pt/Au-4-NCat exhibited up to 35-fold higher TOF (bulk reaction temperature of 25 °C) compared to thermally activated commercial Pt/C (bulk reaction temperature of 120 °C), which It means that solar-induced Pt/Au-4-NCat has a great advantage over existing catalysts that can only be applied under conditions.

After the reaction, Pt/Au-4-NCat can be easily recovered by centrifugation (10,000 rpm, 5 min) and reused in a new reaction with minimal loss of activity, and 13% of the total in TOF after 5 cycles. At a loss, it still achieves >99% conversion. On the other hand, the product yield using the Pt-AuNR catalyst after the first use decreased to 90% in the second cycle ( FIGS. 14 and 15 ).

The catalyst performance in the case of using the THQ derivative was confirmed. The reaction mixture was stirred for different times for each substrate, the THQ derivative mentioned in FIG. 4 . In Figure 4e, the number in parentheses for each compound means the stirring time. At each reaction time, a reaction sample was taken and conversion and yield were measured using an internal NMR standard dibromomethane (2H, 4.93 ppm). All products were determined via NMR spectroscopy without further purification. The number of conversions (TOF) was calculated from the maximum yield at complete conversion time based on the total amount of Pt used in the catalyst.

As shown in Fig. 4e, Pt/Au-4-NCat converted various N-hetero cycles into dehydrogenated products in excellent yield and TOF. However, the bulk-sized substrate of 1-ix did not show detectable dehydrogenation product 2-ix even after 6 h of reaction, because this remarkable specific non-reactivity was limited to the access of the bulky substrate to the intershell cavity for the reaction. to be. In addition, O-containing heterocycles (e.g., tetrahydrobenzofuran, 1-viii) did not react in the dehydrogenation reaction using Pt/Au-4-NCat, and this inactivation is an important Lewis basicity in the noble metal-mediated dehydration step. It appears to be due to a lack of nitrogen.

The high catalytic performance of Pt/Au-4-NCat is interpreted as follows. In the unique and robust complex bilayer structure of Pt/Au-4-NCat, the Pt-modified AuNP units densely formed in the inner and outer layers form a number of plasmon-catalyzed nanocavities within the interlayer region, which is a catalyst limited to numerous nanoscale sizes. By providing a high binding plasmonic hotspot (Fig. 3, confirmed by SERS) at the active site as well as direct contact of the interfacial catalytic site, which can utilize enormous electromagnetic fields and efficiently generate local photothermal effects and high-temperature charge carriers, the confined bilayer nano [Pt/Au]-mediated H ₂ removal from the N-hetero cycle in space was effectively harvested. These structural features synergistically affect the overall catalytic performance of Pt/Au-4-NCat. In particular, the limited space between layers is the most important structural feature in the design of nano-catalosomes, as confirmed from the results. That is, there is a difference in catalytic performance depending on the structure of Pt/Au-1 to 4-NCat, and this shows that Pt/Au-4-NCat with a wide range of limited plasmonic catalyst nano-cavities in the double layer space shows the highest reactivity. In addition, it can be confirmed that the monolayer shell without interlayer space (s-Pt/Au-NCat) exhibits inferior performance, and in the case of a bulk-sized substrate inaccessible to the limited cavity in the bilayer of Pt/Au-4-NCat, the reactivity This low was confirmed.

(Suzuki-Miyaura cross-linking reaction using Pd/Au-nano catalasome)

The application range of nano-catalosomes can be extended to the Suzuki-Miyaura cross-linking reaction using Pd/Au-1 to 4-NCat to generate biaryl by reaction with aryl halide and boric acid. Previously, these reactions were demonstrated under plasmon-induced conditions using simple Pd-AuNR and Pd-AuNP based catalysts.

Pd/Au-1~4-Ncat ([[#] Pd] = 0.01 mol%). Reactions were performed for different times in a dark environment or under light irradiation (300 W Xe lamp with 510 nm filter, power density of incident light is 0.7 W/cm ² ). To investigate the reaction kinetics, samples were collected at each reaction time and GC analysis (YL6500) using a CP7502-Chirasil column (25 m * 0.25 mm * 0.25 um) was performed. After the product was analyzed via NMR spectroscopy without further purification, the water of conversion (TOF) was calculated from the maximum yield for each reaction time based on the total amount of Pd used in the catalyst.

In the test reaction between phenylboronic acid and iodobenzene, Pd/Au-4-NCat (0.01 mol% Pd) maintained the bulk solution temperature at 25°C under sunlight irradiation (300 W Xe lamp, 0.7 W/cm ² ) while providing the conversion to the biaryl product in quantitative yield (TOF=maximum 18s ⁻¹ ). That is, high TOF was achieved even with a small amount of Pd (0.01 mol%). On the other hand, under dark conditions, the conversion yield dropped to 6% or less (FIG. 5 a, b).

Under the same reaction conditions, control catalysts Pd-NCat (Pd bilayer without Au component, TOF =0.9s ^-1 ), a physical mixture of Pd-NCat and Au-4-NCat (TOF=1.2s ^-1 ) and Pd- AuNR (TOF=2.1s ⁻¹ ) showed much inferior performance to Pd/Au-4-NCat (TOF=maximum 18s ⁻¹ ) ( FIG. 5 c ). As can be seen in Fig. 5d, Pd/Au-4-NCat (0.01 mol% Pd) corresponds to a wide range of aryl halides and boronic acid in a short time under sunlight irradiation (300 W Xe lamp, 0.7 W/cm ² ) was converted cleanly to the biaryl product.

Pd/Au-4-NCat achieved a TOF (up to 18s ⁻¹ ) that was 20 times higher than that of Pd-AuNR, the highest among previously used Pd-based catalysts, which in a metal bilayer design, It seems that the catalytic interlayer cavities play an important role in the high reactivity of Pd/Au-4-NCat. That is, the local photothermal effect and abundant thermoelectrons generated in the high-bonding electromagnetic hotspot can be efficiently utilized to promote the cleavage of the [Pd]-catalyzed Cl bond of the aryl halide, which is a basic step in the overall cross-linking reaction.

(Alkyne Cyclization Using Au-Nano Catalosomes)

Au-based catalysts have a special place in organic synthesis due to their selective binding affinity with alkyne groups in the presence of other functional groups, and can cause a variety of unique molecular transformations useful in pharmaceutical and biochemical fields. However, most of these alkyne-activated based chemistries are only possible with non-renewable homogeneous Au(I/III)-complexes or only a few examples of renewable but low-reactive environmentally friendly Au-based catalysts.

The experiment was carried out because it was thought that the low reactivity of [Au]-catalyzed alkyne-activation reaction could be overcome by using interlayer plasmon catalyst nano-cavities for catalysis using the metal double layer structure of Au-1~4-NCat. . Different phenol ester reactions of phenylpropanoic acid 6(i-iv) were chosen.

In a quartz reaction cell, a mixture of substrate 6i-iv (0.2 mmol) and Au-1 to 4Ncat ([Au] = 1 mol%) dispersed in H ₂ O:CH ₃ CN (1:1, 2 ml) was taken. The solution was stirred in a dark environment or under light irradiation (300 W Xe lamp, 510 nm filter, effective power density of incident light 0.7 Wcm ^-2 ) until conversion was completed (confirmed by TLC). After completion of the reaction, the reaction mixture was diluted with diethylether (30 ml) and washed with water (10 ml) and brine (5 ml). The organic layer was separated, dried over anhydrous Na ₂ So ₄ , filtered and evaporated in vacuo. The residue was purified via column chromatography on silica (hexane/ethyl acetate 9:1) to give the cyclized product (7i-iv).

Through the above experiment, in sunlight conditions (300 W Xe lamp, 0.7 W/cm ² ) cyclization through an alkyne moiety and [Au]-pi-acid bond, followed by an aryl moiety of a phenol moiety and a Michael-type CC bond in the molecule It was confirmed that 7(i-iv) was provided in an excellent yield with a conversion rate of 99% through a reaction time of 30 minutes after formation (FIG. 6). In the reaction rates according to the different structures of Au-1 to 4-NCat, the highest reactivity was shown in the case of Au-4-NCat, which proves the effect of the plasmon effect limited to the double layer on the reaction rate (Fig. 6). b)

The consistently high catalytic performance of the nano-catalosome having a metal bilayer structure in various reactions as described above is due to the existence of an abundance in the bilayer structure of the nano-catalosome and the presence of a plurality of controllable nanometer-scale pores (cavities). , it was found that the high level of binding plasmon hotspots in this cavity overlapped well on the limited catalytic site, resulting in improved reaction rates.

The present invention is not limited to the embodiments, but can be manufactured in various different forms, and those of ordinary skill in the art to which the present invention pertains can use other specific forms without changing the technical spirit or essential features of the present invention. It will be appreciated that this may be practiced. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

Claims (20)

A spherical porous amine silica nanoshell with an empty interior and
and a metal double layer comprising a plurality of metal nanoparticles uniformly present on the inner surface and the outer surface of the porous amine silica nanoshell;
a thickness of the outer surface is greater than a thickness of the inner surface;
The thickness of the outer shell of the metal bilayer is 15 nm or less, and the thickness of the inner shell is 12 nm or less, the metal bilayer nano-catalosome.
According to claim 1,
The plurality of metal nanoparticles includes at least one selected from the group consisting of gold (Au), platinum (Pt), and palladium (Pd), a metal double-layered nano-catalosome.
3. The method of claim 2,
The plurality of metal nanoparticles are gold (Au) nanoparticles coated with platinum (Pt), palladium (Pd) or a combination thereof, a metal double-layered nano-catalosome.
A spherical porous amine silica nanoshell with an empty interior and
and a metal double layer comprising a plurality of metal nanoparticles uniformly present on the inner surface and the outer surface of the porous amine silica nanoshell,
A metal double-layered nano-catalosome comprising a plurality of nano-sized pores defined by metal nanoparticles constituting the outer metal layer of the metal double layer and metal nanoparticles constituting the inner metal layer.
5. The method of claim 4,
The size of the pores is determined by the size of the metal nanoparticles constituting the outer metal layer of the metal double layer and the metal nanoparticles forming the inner metal layer of the metal double layer nano-catalosome.
5. The method of claim 4,
The nano-sized pores defined by the metal nanoparticles constituting the outer metal layer and the inner metal layer have a size of 6 nm or less, a metal double-layered nano-catalosome.
5. The method of claim 4,
The plurality of cavities provide a plasmon coupling effect and coupling electromagnetic hotspot, a metal bilayer nano-catalosome.
5. The method of claim 4,
A catalytic reaction takes place in the plurality of cavities, a metal double-layered nano-catalosome.
delete Preparing a spherical porous amine silica nanoshell with an empty interior;
introducing metal nanoparticle seeds to the inner and outer surfaces of the porous amine silica nanoshell by treating the porous amine silica nanoshell with a metal chloride;
coating a tannic acid-Fe (TA-Fe) coordinated polymer layer on the porous amine silica nanoshell into which the metal nanoparticle seeds are introduced; and
growing the metal nanoparticle seeds contained in the porous amine silica nanoshell coated with the tannic acid-Fe coordination polymer layer by treating the metal chloride and the reducing agent;
A method for manufacturing a metal double-layered nano-catalosome comprising a.
11. The method of claim 10,
The step of growing the metal nanoparticle seed is a step of controlling the thickness of the metal double layer by controlling the amount of metal chloride used, a method for producing a metal double layer nano-catalosome.
11. The method of claim 10,
Growing the metal nanoparticle seed;
In the case of using 3 mg of porous amine silica nanoshell having a diameter of 75±3 nm, a method for preparing a metal double-layered nano-catalosome is a step of growing by adding a metal chloride having a concentration of 5 mM to 1.0 ml or less.
11. The method of claim 10,
Growing the metal nanoparticle seed;
In the case of using 3 mg of a porous amine silica nanoshell having a diameter of 75 ± 3 nm, a method for preparing a metal double-layered nano-catalosome is a step of growing by adding a reducing agent having a concentration of 50 mM to 1.0 ml or less.
11. The method of claim 10,
In the method for preparing a nano-catalosome in the form of a metal double layer,
The metal nanoparticles are at least one selected from the group consisting of gold (Au), platinum (Pt), and palladium (Pd) nanoparticles.
11. The method of claim 10,
Coating the tannic acid-Fe (TA-Fe) coordination polymer layer on the porous amine silica nanoshell into which the metal nanoparticle seeds are introduced;
preparing an aqueous solution by dispersing the porous amine silica nanoshell into which the metal nanoparticle seed is introduced in distilled water;
adjusting the pH of the aqueous solution to 8 to 12; and
A method for producing a metal double-layered nano-catalosome, which is a step of mixing tannic acid and iron (III) chloride in the pH-controlled aqueous solution.
11. The method of claim 10,
Growing the metal nanoparticle seed;
Dispersing a porous amine silica nanoshell into which a metal nanoparticle seed coated with a tannic acid-Fe (TA-Fe) coordinated polymer layer is introduced in a PVP aqueous solution; and
A method for producing a metal double-layered nano-catalosome comprising the step of continuously adding metal chloride and a reducing agent to grow metal nano-particle seeds.
11. The method of claim 10,
Growing the metal nanoparticle seed;
The tannic acid-Fe (TA-Fe) coordinated polymer layer is decomposed, and then metal ions are attached to a plurality of metal nanoparticle seeds disposed inside and outside the porous silica nanoshell to grow the metal nanoparticle seeds, the metal double layer A method for manufacturing a nano-catalosome in the form of
18. The method according to any one of claims 10 to 17,
Introducing the metal nanoparticle seed;
The metal chloride is at least one selected from the group consisting of HAuCL ₄ , Na ₂ PdCl ₄ and Na ₂ PtCl ₄ , a method for producing a metal double-layered nano-catalosome.
18. The method according to any one of claims 10 to 17,
growing the metal nanoparticle seed; in
The metal chloride is at least one selected from the group consisting of HAuCL ₄ , Na ₂ PdCl ₄ and Na ₂ PtCl ₄ , a method for producing a metal double-layered nano-catalosome.
18. The method according to any one of claims 10 to 17,
growing the metal nanoparticle seed; in
The reducing agent is hydroquinone, a method for producing a nano-catalosome in the form of a metal double layer.

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