A noble metal nano system and a preparation method and application thereof

By preparing a noble metal nanocavity with one open end, the problem that noble metal nanocages cannot store liquids has been solved, enabling diverse applications, especially in medicine, catalysts, and analytical testing.

CN116604013BActive Publication Date: 2026-03-27SHENZHEN UNIV
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Patent Information

Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2023-05-24
Publication Date
2026-03-27

AI Technical Summary

Technical Problem

Existing precious metal nanocages cannot store liquids, thus limiting their application areas.

Method used

A noble metal nanocavity with one open end was prepared by reducing a noble metal source with a polyol and using a morphology modifier to form a noble metal nanosystem with a accommodating space, which can hold liquids and solids and can be transferred to different substrates.

Benefits of technology

Noble metal nanosystems can hold both liquids and solids, broadening their applications and making them suitable for pharmaceuticals, catalysts, and analytical testing.

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Abstract

The application belongs to the technical field of nanomaterials, and particularly relates to a noble metal nanosystem, a preparation method and application thereof. The noble metal nanosystem comprises an integrated noble metal nanocavity with an open end. In the noble metal nanosystem, the integrated noble metal nanocavity with the open end can form a containing space. The containing space can contain not only solids but also liquids, and has various uses. Meanwhile, research shows that the noble metal nanosystem also has a transferable characteristic, and can be easily transferred from one substrate to another substrate, so that the application range of the noble metal nanosystem can be conveniently widened.
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Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of nanomaterials, and particularly relates to a noble metal nanosystem and a preparation method and application thereof. BACKGROUND

[0002] Noble metal nanomaterials have attracted much attention of researchers due to their special chemical, electrical and optical properties, and have great potential application value in the fields of biological medicine, analysis and detection, catalysis, optoelectronic devices, biosensing, etc. Common noble metal nanomaterials include noble metal nanoparticles, noble metal nanocages, noble metal nanoflowers, noble metal nanowires, noble metal nanonets, etc. These noble metal nanomaterials can be used alone or combined with other materials to form various structures and have different uses.

[0003] Among them, noble metal nanocages are widely studied due to their special cage structure. For example, drugs can be loaded inside hollow noble metal nanocages, or biological materials can be coated on the surface of hollow noble metal nanocages. However, the existing noble metal nanocages generally have a hollow structure, and only substances with a certain particle size can be loaded inside, and liquids cannot be stored, so the application field is limited. SUMMARY

[0004] The application aims to provide a noble metal nanosystem and a preparation method and application thereof, and aims to solve the problem that noble metal nanocages cannot store liquids.

[0005] To achieve the above application purposes, the technical solutions adopted by the application are as follows:

[0006] In a first aspect, the application provides a noble metal nanosystem, which comprises an integrated noble metal nanocavity with one end open.

[0007] In the noble metal nanosystem of the embodiments of the application, the noble metal nanocavity with one end open can form a containing space. In addition to being able to place solids, the containing space can also place liquids, and has various uses. At the same time, it is found that the noble metal nanosystem also has the characteristic of being transferable, and can be easily transferred from one substrate to another substrate, so as to conveniently broaden its application range.

[0008] In a second aspect, the application provides a preparation method of a noble metal nanosystem, comprising:

[0009] In a solution system, polyols are mixed with noble metal sources and morphology adjusting agents, and a reduction reaction is performed to obtain a noble metal nanosystem; the noble metal nanosystem comprises an integrated noble metal nanocavity with one end open.

[0010] The polyol is used as a reducing agent in the embodiment of the application, the noble metal source can be reduced to noble metal, and the noble metal formed in the reduction process can form a noble metal nanosystem with a special structure under the action of a morphology adjusting agent. The preparation method is simple, has good repeatability, is flexible, and the noble metal nanosystem prepared has a solid structure.

[0011] The noble metal nanosystem prepared by the method is an integrated noble metal nanocavity with one end open, can form a containing space, and can contain a liquid in addition to a solid, and has various uses.

[0012] In a third aspect, the application provides an application of the noble metal nanosystem, and the application is that the noble metal nanosystem is applied to the preparation of medicine, the preparation of a catalyst, or analysis and detection.

[0013] The noble metal nanosystem of the embodiment of the application has a cavity structure capable of containing a liquid and a solid, can be used for the preparation of medicine, the preparation of a catalyst, and analysis and detection, and has a wide application range. BRIEF DESCRIPTION OF DRAWINGS

[0014] In order to more clearly illustrate the technical solutions in the embodiments of the application, the drawings needed to be used in the embodiments or the prior art description will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the application, and other drawings can be obtained by those skilled in the art without any creative effort on the basis of these drawings.

[0015] Figure 1 A schematic diagram of the chemical reduction, transfer, liquid filling, and top wall covering process of the noble metal nanosystem;

[0016] Figure 2 A scanning electron microscope (SEM) image of the gold nanosystem in Example 1;

[0017] Figure 3 An atomic force microscope (AFM) image of the gold nanosystem in Example 1;

[0018] Figure 4 A schematic diagram of the depth of the containing space and the height of the gold side wall of the gold nanosystem in Example 1;

[0019] Figure 5 A scanning electron microscope (SEM) image of the gold nanosystem in Example 2;

[0020] Figure 6 An optical microscope photograph of the gold nanosystem covering gold nanosheets in Example 2;

[0021] Figure 7 SEM and cross-sectional TEM photographs of the gold nanosystem covering gold nanosheets in Example 2;

[0022] Figure 8 An electron microscope image of the reaction product in Example 3.

[0023] Figure 9 An electron microscope image of the reaction product in Example 4. DETAILED DESCRIPTION

[0024] In order to make the technical problems to be solved, technical solutions and beneficial effects of the present application clearer, the present application will be further described in detail below in conjunction with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and should not be used to limit the present application.

[0025] In the present application, the term "and / or" describes the association relationship of the associated objects, which means that there can be three kinds of relationships, for example, A and / or B can mean that A exists alone, A and B exist together, and B exists alone. Wherein A and B can be singular or plural. The character " / " generally represents an "or" relationship between the associated objects before and after it.

[0026] In the present application, "at least one" means one or more, and "multiple" means two or more. "At least one" or similar expressions refer to any combination of these items, including any combination of single item or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can mean a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, wherein a, b, and c can be single or multiple.

[0027] It should be understood that in various embodiments of the present application, the size of the sequence number of the above-mentioned processes does not mean the order of execution, and part or all steps can be executed in parallel or in sequence. The execution order of each process should be determined according to its function and inherent logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0028] The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. The singular forms "a", "said" and "the" used in the embodiments of the present application and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise.

[0029] The weight of the related components mentioned in the embodiment specification of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of each component. Therefore, as long as the content of the related components in the embodiment specification of the present application is enlarged or reduced in proportion, it is within the scope disclosed in the embodiment specification of the present application. Specifically, the mass mentioned in the embodiment specification of the present application can be μg, mg, g, kg and other mass units commonly known in the chemical field.

[0030] The terms "first", "second" are only for descriptive purposes, used to distinguish objects such as substances from each other, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. For example, without departing from the scope of the present application, the first XX can also be referred to as the second XX, and similarly, the second XX can also be referred to as the first XX. Therefore, the features defined with "first", "second" can explicitly or implicitly include one or more of the features.

[0031] The first aspect of the embodiment of the present application provides a noble metal nanosystem, which comprises an integrated, one-end-open noble metal nanocavity. In the embodiment of the present application, "integrated" means that the parts of the structure cannot be separated from each other. "Cavity" refers to a structure that is closed and isolated from the outside, while the inside is hollow. "Nanocavity" refers to a cavity with at least one of its depth, circumference, side length, diameter, etc. in the nanometer scale, having a very small volume.

[0032] In the noble metal nanosystem of the embodiment of the present application, the one-end-open noble metal nanocavity can form a containing space. In addition to placing solids, the containing space can also place liquids, with diverse uses. At the same time, it is found that the noble metal nanosystem also has the characteristics of being transferable, and can be easily transferred from one substrate to another, which can facilitate the expansion of its application range.

[0033] In some embodiments, the volume of the noble metal nanocavity is 0.5-3 fL (1 fL = 10 -15 L), and optionally 0.8-2 fL. The noble metal nanosystem is a small container with a small volume, which can be used for placing micro-liquids or micro-solids.

[0034] In some embodiments, the depth of the noble metal nanocavity is 20-50 nm, and optionally 30-50 nm. The depth of the cavity refers to the distance from the opening of the cavity to its bottom surface. In the noble metal nanosystem of the embodiment of the present application, the depth of the cavity is in the nanometer size, which is sufficient to place micro-liquids or micro-solids.

[0035] In some embodiments, the noble metal nanosystem comprises a noble metal nanobase and a noble metal nanowall, which enclose the noble metal nanocavity. Wherein, the "wall" refers to the surrounding side of the noble metal nanosystem; the "nanowall" refers to a wall structure with nanoscale size, i.e., at least one of the length, height, width, etc. of the wall is in nanoscale.

[0036] In some embodiments, the shape of the noble metal nanobase comprises one or more of a circle, an ellipse, a polygon, and an irregular shape, but is not limited thereto. The noble metal nanobase can be various shapes, which enriches the morphology of the noble metal nanocavity and facilitates the application of the noble metal nanosystem in different scenarios.

[0037] In some embodiments, the height of the noble metal nanowall is 20-80 nm, and optionally 30-60 nm. The height of the noble metal nanowall refers to the distance from the end of the noble metal nanowall in contact with the noble metal nanobase to the opposite end. Generally, the height of the noble metal nanowall is greater than the depth of the cavity.

[0038] In some embodiments, the noble metal nanosystem comprises at least one bottom side, and the length of any one of the bottom sides is 2-20 μm, and optionally 5-10 μm. The bottom side of the noble metal nanosystem refers to the side of the noble metal nanowall in contact with the noble metal nanobase, and the face formed by all the bottom sides is the noble metal nanobase. The bottom side has a suitable length, which helps to increase the volume of the noble metal nanosystem and maintain the stability of the structure of the noble metal nanosystem.

[0039] In some embodiments, the number of bottom sides is greater than or equal to 3, and optionally 3-10, and further optionally 3-6. The shape of any one of the bottom sides can be linear, arc-shaped, or other irregular shape. According to the number and shape of the bottom sides, noble metal nanosystems of different shapes can be formed, which enriches the shapes of the noble metal nanosystems. In some embodiments, the noble metal nanosystem further comprises a top wall covering the opening of the noble metal nanocavity. By covering the opening of the noble metal nanocavity with the top wall, the noble metal nanosystem can have a completely closed cavity structure, which can better place objects in the cavity.

[0040] In some embodiments, the top wall comprises one or more of noble metal nanosheet, graphene, glass, silicon nitride, silicon, polydimethylsiloxane (PDMS), polymethyl methacrylate (PMMA). The top wall used to cover the opening of the noble metal nanocavity can be made of noble metal material as the noble metal nanoside wall and the noble metal bottom disc, or can be made of other various materials, which can be hard or flexible, and the optional materials are extensive. Graphene, glass, silicon nitride, silicon, PDMS, PMMA, etc. can be in the form of sheet or film.

[0041] In some embodiments, the noble metal comprises one or more of gold, silver, platinum, and optionally comprises gold.

[0042] The second aspect of the embodiments of the present application provides a preparation method of a noble metal nanosystem, comprising:

[0043] In a solution system, polyol is mixed with noble metal source and morphology regulator to perform reduction reaction to obtain noble metal nanosystem; the noble metal nanosystem comprises integrated noble metal nanocavity with one end open.

[0044] The embodiments of the present application use polyol as reducing agent to reduce noble metal source into noble metal, and under the action of morphology regulator, the noble metal formed in the reduction process can form noble metal nanosystem with special structure. The preparation method is simple, has good repeatability, strong flexibility, and the noble metal nanosystem prepared has a solid structure.

[0045] The noble metal nanosystem prepared by the method comprises integrated noble metal nanocavity with one end open, can form a containing space, which can contain not only solids but also liquids, and has various uses.

[0046] In some embodiments, the temperature of the reduction reaction is 75-100°C, and optionally is 80-100°C. The time of the reduction reaction is 7-70h, and optionally is 18-24h. The reaction at a higher temperature for a period of time can make the reduction reaction of polyol and noble metal source have a suitable reaction rate.

[0047] In some embodiments, the polyol comprises one or more of ethylene glycol, propylene glycol, and pentanediol. Such polyol can reduce noble metal source and help to form noble metal nanosystem with specific structure.

[0048] In some embodiments, the noble metal source comprises one or more of HAuCl4, AgNO3, and H2PtCl6.

[0049] In some embodiments, the ratio of the polyol to the noble metal source is (20-15000) mL: 1 mmol, optionally (60-5000) mL: 1 mmol. At a suitable ratio, the polyol can effectively reduce the noble metal source.

[0050] In some embodiments, the morphology regulator comprises one or more of KCl, KBr, NaCl, NaBr, optionally a mixture of KCl and KBr. In the mixture of KCl and KBr, KCl and KBr can be mixed in any ratio, for example, the molar ratio of KCl to KBr can be set to 1:(1-5). In the reduction reaction, such morphology regulator can control the shape and size of the reduction product, and help to form noble metal nanosystems with desired structures.

[0051] In some embodiments, the molar ratio of the noble metal source to the morphology regulator is 1:(0.02-0.5), optionally 1:(0.05-0.2). At a suitable amount of the morphology regulator, the morphology regulator can control the shape and size of the reduction product, and help to form noble metal nanosystems with desired structures. And by adjusting the amount of the morphology regulator, the shape and size of the noble metal nanosystems can be flexibly controlled.

[0052] In some embodiments, in the solution system, the concentration of the noble metal source is 0.01-50 mM, optionally 0.06-50 mM, and further optionally 1-10 mM.

[0053] In some embodiments, the method for preparing the noble metal nanosystems comprises:

[0054] In 10-30 mL of polyol, 10-1000 μL of noble metal source solution with a concentration of 0.2-0.5 M and 10-1000 μL of morphology regulator solution with a concentration of 10-100 mM are added, and a reduction reaction is performed to obtain noble metal nanosystems.

[0055] By mixing the polyol, the noble metal source solution and the morphology regulator solution, a solution system containing the polyol, the noble metal source and the morphology regulator can be formed.

[0056] Any of the above-mentioned solutions (solution system, noble metal source solution, morphology regulator solution, etc.) can independently use one or more of water and ethanol as the solvent, and optionally use water as the solvent.

[0057] In some embodiments, the preparation method of the noble metal nanosystem further includes adding a first substrate to a solution system. This step can be performed before the reduction reaction. By adding the first substrate to the solution system in which the reduction reaction is taking place, the noble metal nanosystem formed during the reduction reaction can adhere to the first substrate, thereby facilitating the transfer of the noble metal nanosystem. Furthermore, studies have found that some noble metal nanosystems tend to adhere to the first substrate with the open side of the noble metal nanocavity, forming a closed cavity between the noble metal nanosystem and the first substrate, such as... Figure 1 As shown in A1. Meanwhile, in some noble metal nanosystems, the opening of the noble metal nanocavity faces away from the first substrate.

[0058] After the reduction reaction step, the first substrate can be pressed with the second substrate. The pressing process can be light, typically with a pressure less than 50 N, and the pressing time can be 3–5 minutes. In practice, after the reduction reaction is complete, the first substrate can be removed, dried, and then the first substrate can be pressed with the second substrate. By pressing the first substrate with the second substrate, the noble metal nanosystem attached to the first substrate can be transferred to the second substrate, and the orientation of the noble metal nanosystem changes after the transfer. For example, for a noble metal nanosystem that is attached to the first substrate... Figure 1 In the case of A1, after being transferred to the second substrate, the noble metal chassis is attached to the second substrate, and the opening of the noble metal nanocavity faces upwards, as shown in the example. Figure 1 As shown in A2. Thus, liquids or other substances can be placed within the cavities of noble metal nanosystems, such as... Figure 1 As shown in A3. After placing liquids or other substances in the cavity, the opening of the cavity can be covered by a top wall, such as... Figure 1 As shown in A4 of the document.

[0059] Alternatively, in a noble metal nanocavity system where the opening of the noble metal nanocavity faces away from the first substrate, after transfer to the second substrate, the noble metal chassis attaches to the second substrate, with the opening of the noble metal nanocavity facing the second substrate. Subsequently, it can be transferred to other substrates or instruments through multiple pressing operations as needed. In some embodiments, the first and second substrates independently comprise one or more of glass, silicon nitride, silicon, PDMS, and PMMA. The first and second substrates can each independently be a sheet or a thin film.

[0060] The third aspect of this application provides an application of the above-described noble metal nanosystem, which is to use the above-described noble metal nanosystem in the manufacture of pharmaceuticals, the manufacture of catalysts, or in analytical detection.

[0061] The noble metal nanosystem of the embodiment of the present application has a cavity structure capable of placing liquid and solid, and can be used for manufacturing medicine, manufacturing catalyst, and performing analysis and detection, etc., and has a wide range of applications.

[0062] The application of manufacturing medicine includes loading drugs by using the noble metal nanosystem, and applying the noble metal nanosystem as a targeted therapeutic agent, a photothermal therapeutic agent, etc.

[0063] The application of manufacturing catalyst can include directly using the noble metal nanosystem as a catalyst, loading other metals, metal oxides, non-metals or non-metal oxides, etc. by using the noble metal nanosystem to manufacture different catalysts, or compounding the noble metal nanosystem with other metals, metal oxides, non-metals or non-metal oxides in other forms to obtain various catalysts for different purposes.

[0064] The application of analysis and detection includes using the noble metal nanosystem as a TEM (transmission electron microscope) liquid pool (observation chamber), a microscope liquid pool (observation chamber), a Raman spectrum detection liquid pool, etc., which can place liquid (such as intracellular liquid and other liquid) to perform TEM observation, microscope observation and Raman spectrum test.

[0065] The following will be described in combination with specific embodiments.

[0066] Embodiment 1

[0067] The embodiment provides a gold nanosystem, and a preparation method thereof is as follows:

[0068] Chemical growth: 10 μL of HAuCl4 solution with a concentration of 0.2 M is added into 10 mL of EG (ethylene glycol), and 10 μL of mixed solution of KCl and KBr with a concentration of 10 mM (the molar ratio of KCl to KBr is 1:2) is added to obtain a reaction liquid. A clean glass substrate is added into the reaction liquid, and the reaction is performed at 80°C for 20 hours. After the reaction is completed, the gold nanosystem is grown on the glass substrate.

[0069] The glass substrate is taken out from the reaction mixture, and the PDMS flexible substrate is pressed onto the glass substrate after drying. The PDMS flexible substrate is taken off after about 3 min, so as to realize the transfer of the gold nanosystem.

[0070] The scanning electron microscope picture of the gold nanosystem of the embodiment is shown in Figure 2 It can be seen that the gold nanosystem includes a gold bottom surface and a gold side wall arranged on the gold bottom surface, the gold bottom surface is attached to the gold side wall, and the gold bottom surface and the gold side wall enclose a cavity which is close to an equilateral triangle and has an open top, and can be used as a containing space. The gold nanosystem is measured, and its size is as shown in Figure 3 and Figure 4The results show that the side length of the gold sidewall of the gold nanosystem is about 10 μm, the depth of the accommodation space surrounded by the gold bottom surface and the gold sidewall is about 31.9 nm, and the maximum height of the gold sidewall is about 50 nm. According to the calculation of each size, the volume of the cavity is about 1.8 fL.

[0071] Example 2

[0072] This example provides a gold nanosystem, and a preparation method thereof is as follows:

[0073] Chemical growth: 1000 μL of 0.5 M HAuCl4 solution was added into 30 mL of EG, 1000 μL of 100 mM KCl and KBr mixed solution (the molar ratio of KCl and KBr is 1:2) was added to obtain a reaction solution. A clean glass substrate was added into the reaction solution, and the reaction was carried out at 100 °C for 20 hours. After the reaction was completed, the gold nanosystem was grown on the glass substrate.

[0074] The glass substrate was taken out of the reaction mixture, and then the PDMS flexible substrate was pressed onto the glass substrate after drying. After about 5 min, the PDMS flexible substrate was taken off, and the transfer of the gold nanosystem was realized.

[0075] The scanning electron microscope picture of the gold nanosystem of this example is shown in Figure 5 It can be seen that the gold nanosystem includes a gold bottom surface and a gold sidewall arranged on the gold bottom surface, the gold bottom surface is attached to the gold sidewall, and the gold bottom surface and the gold sidewall surround a cavity which is close to an isosceles hexagon and has an open top, which can be used as an accommodation space. The open top of the accommodation space is covered by a gold nanosheet, as shown in Figure 6 , and a closed cavity can be formed.

[0076] The TEM picture of the gold nanosystem after covering the gold nanosheet is shown in Figure 7 . Figure 7 Figure a in shows that in the TEM environment, the cavity structure under the gold nanosheet can be clearly observed. Figure 7 Figure b is a cross-sectional picture, in which the black area is Au, and the middle white area is the cavity, further verifying the existence of the cavity structure in the gold nanosystem. Therefore, if a liquid or other sample is placed in the cavity, the sample can be very conveniently observed by TEM. That is, the gold nanosystem can be used as a TEM liquid cell.

[0077] Example 3

[0078] The difference between this example and Example 1 is that the raw material does not contain KCl.

[0079] Specifically, 10 μL of HAuCl4 solution with a concentration of 0.2 M was added into 10 mL of EG, and 10 μL of KBr solution with a concentration of 10 mM was added to obtain a reaction solution. A clean glass substrate was added into the reaction solution, and the reaction was carried out at 80°C for 20 hours.

[0080] After the reaction was completed, the glass substrate was taken out for observation. As shown in FIG. 1, the product contained a small amount of gold nano-systems with cavity structures of various shapes, such as approximately triangular and hexagonal shapes, and also contained other impurity particles without cavity structures. The results showed that a small amount of gold nano-systems with cavity structures could be formed in the reaction process by using KBr as a morphology regulator alone, and there were many impurities. Figure 8

[0081] Example 4

[0082] The difference between this example and Example 1 is that KBr is not contained in the raw materials.

[0083] Specifically, 10 μL of HAuCl4 solution with a concentration of 0.2 M was added into 10 mL of EG, and 10 μL of KCl solution with a concentration of 10 mM was added to obtain a reaction solution. A clean glass substrate was added into the reaction solution, and the reaction was carried out at 80°C for 20 hours.

[0084] After the reaction was completed, the glass substrate was taken out for observation. As shown in FIG. 2, the product contained a small amount of gold nano-systems with cavity structures of various shapes, such as approximately triangular and hexagonal shapes, and also contained a large amount of impurity particles without cavity structures. The results showed that a small amount of gold nano-systems with cavity structures could be formed in the reaction process by using KCl as a morphology regulator alone, and there were many impurities. Figure 9

[0085] Comparative Example 1

[0086] The difference between this comparative example and Example 1 is that the reaction temperature was reduced to 70°C.

[0087] Specifically, 10 μL of HAuCl4 solution with a concentration of 0.2 M was added into 10 mL of EG, and 10 μL of KCl and KBr mixed solution (the mass ratio or molar ratio of KCl to KBr was 1:2) with a concentration of 10 mM was added to obtain a reaction solution. A clean glass substrate was added into the reaction solution, and the reaction was carried out at 70°C for 20 hours. After the reaction was completed, the glass substrate was taken out for observation, and it was found that no product was generated, which reflected that the reaction could not be carried out at low temperature and the target product could not be obtained.

[0088] Comparative Example 2

[0089] The difference between this comparative example and Example 1 is that the reaction time was reduced to 6 hours.

[0090] ​​Specifically, 10 μL of HAuCl4 solution with a concentration of 0.2 M was added into 10 mL of EG, 10 μL of KCl and KBr mixed solution with a concentration of 10 mM (mass ratio or molar ratio of KCl to KBr was 1:2) was added to obtain a reaction solution. A clean glass substrate was added into the reaction solution, and the reaction was carried out at 80°C for 6 hours. After the reaction was completed, the glass substrate was taken out and observed, and it was found that no product was generated.

[0091] Comparative Example 3

[0092] The difference between the present comparative example and Example 1 is that the reaction time was increased to 3 days (72 hours).

[0093] Specifically, 10 μL of HAuCl4 solution with a concentration of 0.2 M was added into 10 mL of EG, 10 μL of KCl and KBr mixed solution with a concentration of 10 mM (mass ratio or molar ratio of KCl to KBr was 1:2) was added to obtain a reaction solution. A clean glass substrate was added into the reaction solution, and the reaction was carried out at 80°C for 3 days. After the reaction was completed, the glass substrate was taken out and observed, and it was found that the obtained product contained a large amount of gold nanosheets without cavities, and some gold nanosheets contained cavities, but the volume of the cavities was very small and difficult to be used for placing liquid.

[0094] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Any modification, equivalent replacement and improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a noble metal nanosystem, characterized in that, include: In a solution system, a polyol is mixed with a noble metal source and a morphology modifier, and then a first substrate is added to the solution system to carry out a reduction reaction to obtain a noble metal nanosystem; the noble metal nanosystem includes an integrated noble metal nanocavity with one open end; The reduction reaction is carried out at a temperature of 75~100℃ for 7~70h. The polyols include one or more of ethylene glycol, propylene glycol, and pentanediol; The precious metal source includes one or more of HAuCl4, AgNO3, and H2PtCl6; The ratio of the polyol to the noble metal source is (20~15000) mL: 1 mmol; The morphology modifier includes one or more of KCl, KBr, NaCl, and NaBr; The molar ratio of the noble metal source to the morphology modifier is 1:(0.02~0.5). In the solution system, the concentration of the noble metal source is 0.01~50mM.

2. The preparation method according to claim 1, characterized in that, The reduction reaction is carried out at a temperature of 80~100℃ for 18~24 hours. And / or, the ratio of the polyol to the noble metal source is (60~5000) mL: 1 mmol; And / or, the molar ratio of the noble metal source to the morphology modifier is 1:(0.05~0.2). And / or, in the solution system, the concentration of the noble metal source is 0.06~50mM.

3. A noble metal nanosystem, characterized in that, The noble metal nanosystem includes an integrated noble metal nanocavity with one open end, and the noble metal nanosystem is prepared by the preparation method described in claim 1 or 2.

4. The noble metal nanosystem according to claim 3, characterized in that, The volume of the noble metal nanocavity is 0.5~3fL; And / or, the depth of the noble metal nanocavity is 20~50nm; And / or, the noble metal nanosystem includes a noble metal nanobottom and noble metal nanosidewalls, the noble metal nanobottom and noble metal nanosidewalls forming the noble metal nanocavity.

5. The noble metal nanosystem according to claim 3 or 4, characterized in that, The volume of the noble metal nanocavity is 0.8~2fL; And / or, the depth of the noble metal nanocavity is 30~50nm.

6. The noble metal nanosystem according to claim 4, characterized in that, The height of the noble metal nano-sidewalls is 20~80nm; And / or, the noble metal nanosystem further includes a top wall that covers the opening of the noble metal nanocavity; And / or, the precious metal includes one or more of gold, silver, and platinum.

7. The noble metal nanosystem according to claim 6, characterized in that, The height of the noble metal nano-sidewalls is 30~60nm; And / or, the top wall comprises one or more of noble metal nanosheets, graphene, glass, silicon nitride, silicon, polydimethylsiloxane, and polymethyl methacrylate.

8. An application of a noble metal nanosystem, characterized in that, The application refers to using the noble metal nanosystem described in any one of claims 3 to 7 in the manufacture of pharmaceuticals, the manufacture of catalysts, or in analytical testing.

Citation Information

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