WO2022016741A1 - 一种尺寸可调的金纳米粒子的制备方法 - Google Patents

一种尺寸可调的金纳米粒子的制备方法 Download PDF

Info

Publication number
WO2022016741A1
WO2022016741A1 PCT/CN2020/126905 CN2020126905W WO2022016741A1 WO 2022016741 A1 WO2022016741 A1 WO 2022016741A1 CN 2020126905 W CN2020126905 W CN 2020126905W WO 2022016741 A1 WO2022016741 A1 WO 2022016741A1
Authority
WO
WIPO (PCT)
Prior art keywords
gold nanoparticles
aqueous solution
reaction
polyvinylpyrrolidone
glycerol
Prior art date
Application number
PCT/CN2020/126905
Other languages
English (en)
French (fr)
Inventor
徐敏敏
魏倩
姚建林
Original Assignee
苏州大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 苏州大学 filed Critical 苏州大学
Publication of WO2022016741A1 publication Critical patent/WO2022016741A1/zh

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/065—Spherical particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates to the technical field of nanoparticle preparation, in particular to a preparation method of size-adjustable gold nanoparticles.
  • Nanomaterials generally refer to materials whose three-dimensional dimensions have at least one dimension at the nanoscale. Compared with macroscopic metal particles, nano-sized metal particles have unique thermal, optical, electrical, magnetic and catalytic properties due to their small size effect, surface effect and quantum size effect.
  • the special properties of metal nanoparticles largely depend on their size, shape, and aggregation state. Because nanoparticles of different sizes exhibit different properties, they are crucial in basic science and technology fields such as optics, electronics, and catalysis. Among them, the size effect of gold nanoparticles has been widely studied. Gold nanoparticles with different sizes show different colors, and the position of the surface plasmon resonance peak will red-shift with the particle size.
  • top-down and bottom-up There are two main approaches for synthesizing nanostructures: top-down and bottom-up.
  • the top-down approach is to obtain small-sized nanoparticles by cutting or pulverizing bulk materials, usually requiring large equipment.
  • Bottom-up is the construction from the bottom, that is, atoms, molecules or nanoparticles are gradually piled up through particle-to-particle interactions or self-assembly. From the perspective of scientific research in chemical laboratories, more bottom-up research methods are used.
  • the Turkevich-Frens method is currently the most commonly used method for preparing gold nanoparticles, and the size of the particles can be controlled. This method was pioneered by Turkevich in 1951 and improved by Frens in 1973. The method controls the particle size by adjusting the ratio of sodium citrate to chloroauric acid. Although this method is classic, it has certain limitations, such as: the reaction is carried out in a boiling water system, requiring high-temperature heating equipment and a condensation reflux device. Therefore, limited by the number of devices, the synthesis of nanoparticles cannot be carried out in large quantities. In addition, in order to ensure the safety of heating experiments, personnel are usually required to be on duty, which brings certain troubles to the convenience of synthesis.
  • the House-Schiffrin method is also a classic method for synthesizing gold nanoparticles.
  • the size of the nanoparticles prepared by this method is very small.
  • phase transfer is used, organic reagents are introduced, and an ice bath is required, and the operation steps are complicated.
  • thiol is also used, and the thiol group in the thiol can be strongly adsorbed on the surface of gold, which is not conducive to the subsequent application of gold nanoparticles.
  • the technical problem to be solved by the present invention is to provide a preparation method of size-adjustable gold nanoparticles.
  • the preparation method has simple steps, can be carried out under normal temperature and pressure, does not require complicated devices, and the size of the synthesized gold nanoparticles can be adjusted. control.
  • the present invention provides the following technical solutions:
  • the invention provides a method for preparing gold nanoparticles with adjustable size, comprising the following steps:
  • the preparation solute is a mixed aqueous solution of glycerol, ascorbic acid, sodium citrate and polyvinylpyrrolidone;
  • chloroauric acid aqueous solution to the mixed aqueous solution for reaction to obtain gold nanoparticles; wherein, the concentration of each component in the reaction solution is: glycerol 5v% ⁇ 80v%, ascorbic acid 1wt% ⁇ 10wt%, sodium citrate 0.05wt%-0.5wt%, polyvinylpyrrolidone 0.05wt%-0.5wt%, chloroauric acid 0.01wt%-0.1wt%.
  • step S1 the molecular weight of the polyvinylpyrrolidone is 5000-40000.
  • step S1 the preparation method of the mixed aqueous solution is as follows: glycerol, ascorbic acid, sodium citrate and polyvinylpyrrolidone are respectively prepared into aqueous solutions, and then various aqueous solutions are mixed to obtain the mixed aqueous solution.
  • step S2 the reaction condition is room temperature.
  • step S2 the molar ratio of chloroauric acid to glycerol in the reaction solution is 1:272-1:43580.
  • step S2 the molar ratio of chloroauric acid to ascorbic acid in the reaction solution is 1:23-1:2338.
  • step S2 the reaction time is 1-10 min.
  • step S2 after the reaction is completed, the precipitate is collected and washed to obtain gold nanoparticles.
  • the gold nanoparticles are spherical and have a size of 40 nm to 300 nm.
  • the reagents used are common reagents, which are cheap and easy to buy, and the reagents glycerol, ascorbic acid, sodium citrate, and polyvinylpyrrolidone used in addition can be used as food additives. No pollution to the environment and no harm to the human body.
  • the preparation method of the present invention is carried out under normal temperature and pressure, and the required instruments and equipment are simple, such as commonly used glass reaction bottles, disposable Pasteur droppers and pipettes, and do not require risky heating devices such as autoclaves and complex glass instruments such as reflux condensers. Without the limitations of instruments and equipment, the gold nanoparticles can be easily synthesized in batches.
  • the operations involved in the synthesis experiment of the present invention are all simple operations, and only the most conventional steps such as dropwise addition, stirring, and centrifugation are required.
  • reaction time Due to the concentration difference of glycerol, the reaction time varies from 1 to 10 minutes. Compared with many nanoparticles, the synthesis process cannot be completed for several hours or even a day, the nanoparticle of the present invention takes less time and is convenient for practical application.
  • gold nanoparticles have a long history and involve many fields. When gold nanoparticles are combined with magnetic nanoparticles, they can be used for targeted drug-loaded therapy of tumors. Gold nanoparticles with surface plasmon vibration peaks in the infrared region can also be used for cancer hyperthermia applications. In the field of spectroscopy, gold nanoparticles are stable substrates for surface-enhanced Raman spectroscopy, which can effectively detect trace substances and dynamically monitor chemical reaction processes. In the field of catalysis, gold nanoparticles are widely used in oxygen reduction reactions, CO catalytic reactions, fuel cell catalysts, etc.
  • Fig. 1 is the scanning electron microscope picture of gold nanoparticles prepared in Example 1 of the present invention.
  • Fig. 2 is the scanning electron microscope image of gold nanoparticles prepared in Example 2 of the present invention.
  • Example 3 is a scanning electron microscope image of gold nanoparticles prepared in Example 3 of the present invention.
  • Fig. 4 is the ultraviolet-visible absorption spectrogram of gold nanoparticles prepared in Example 1 of the present invention.
  • Fig. 5 is the ultraviolet-visible absorption spectrogram of gold nanoparticles prepared in Example 2 of the present invention.
  • FIG. 6 is an ultraviolet-visible absorption spectrum diagram of gold nanoparticles prepared in Example 3 of the present invention.
  • the Turkevich-Frens method needs to be carried out in a boiling water system, and requires high-temperature heating equipment and a condensation reflux device. ; Limited by the number of devices, the synthesis of nanoparticles cannot be carried out in large quantities.
  • the nanoparticles prepared by the House-Schiffrin method are very small in size, phase transfer is used in the preparation process, organic reagents are introduced, and an ice bath is required, and the operation steps are cumbersome; It can be strongly adsorbed on the surface of gold, which is not conducive to the subsequent application of gold nanoparticles.
  • the preparation solute is a mixed aqueous solution of glycerol, ascorbic acid, sodium citrate and polyvinylpyrrolidone;
  • chloroauric acid aqueous solution to the mixed aqueous solution for reaction to obtain gold nanoparticles; wherein, the concentration of each component in the reaction solution is: glycerol 5v% ⁇ 80v%, ascorbic acid 1wt% ⁇ 10wt%, sodium citrate 0.05wt%-0.5wt%, polyvinylpyrrolidone 0.05wt%-0.5wt%, chloroauric acid 0.01wt%-0.1wt%.
  • the sodium citrate in the present invention is not used as a reducing agent, but ascorbic acid is additionally added as a reducing agent, which can reduce chloroauric acid at normal temperature to obtain gold nanoparticles, so the reaction of the present invention is.
  • the conditions are very mild, and it can be carried out at normal temperature and pressure, which is more green, energy-saving and environmentally friendly; the required instruments and equipment are also very simple, such as commonly used glass reaction bottles, disposable Pasteur pipettes and pipettes, and no high-pressure reaction is required. Risky heating devices such as kettles and complicated glass instruments such as reflux condensers; and without the limitations of instruments and equipment, the gold nanoparticles can be easily synthesized in batches.
  • the molar ratio of chloroauric acid to ascorbic acid in the reaction solution is 1:23-1:2338.
  • the added sodium citrate mainly plays the role of preventing the aggregation of the synthesized gold nanoparticles.
  • the citrate generated by the ionization of sodium citrate will be adsorbed on the surface of the gold nanoparticles to form a protective layer, so that the surface of the gold nanoparticles is negatively charged. Due to electrostatic repulsion, the gold nanoparticles can be stably dispersed in the solution without aggregation. Shen, which improves the stability of gold nanoparticles.
  • Polyvinylpyrrolidone is a water-soluble polymer compound, which can be adsorbed on the surface of gold nanoparticles, surround the gold nanoparticles, and form a polymer protective film, preventing the direct contact between the gold nanoparticles, thereby further significantly increased the stability of gold nanoparticles.
  • the molecular weight of the polyvinylpyrrolidone used is preferably 5,000-40,000, more preferably 10,000.
  • the present invention skillfully utilizes the characteristic that the higher the viscosity of the system, the slower the growth of the nanoparticles, and the larger the size of the prepared nanoparticles, and a certain amount of glycerol is added to the system to adjust the viscosity of the solution, so that it is possible to adjust the viscosity of the solution.
  • Dimensions of synthesized gold nanoparticles Preferably, the molar ratio of chloroauric acid to glycerol in the reaction solution is 1:272-1:43580.
  • the reaction time varies from 1 to 10 minutes, and the time-consuming is short, which is convenient for practical application.
  • the precipitate can be collected by centrifugation, and then washed and dried several times to obtain gold nanoparticles.
  • the gold nanoparticles synthesized by the present invention are spherical, with a size of 40 nm to 300 nm, and have good dispersibility (see accompanying drawings 1-3).
  • the gold nanoparticles synthesized in the present invention are widely used, for example, combined with magnetic nanoparticles, they can be used for targeted drug-loaded treatment of tumors; the gold nanoparticles with surface plasmon vibration peaks in the infrared region can also be used for cancer hyperthermia Application:
  • gold nanoparticles are stable surface-enhanced Raman spectroscopy substrates, which can effectively detect trace substances and dynamically monitor chemical reaction processes; in the field of catalysis, they can be used in oxygen reduction reactions, CO catalytic reactions, fuel cells catalyst, etc.
  • a method for synthesizing gold nanoparticles with adjustable size the steps are as follows:
  • a method for synthesizing gold nanoparticles with adjustable size the steps are as follows:
  • a method for synthesizing gold nanoparticles with adjustable size the steps are as follows:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

本发明公开了一种尺寸可调的金纳米粒子的制备方法，包括以下步骤：S1.配制溶质为甘油、抗坏血酸、柠檬酸钠和聚乙烯吡咯烷酮的混合水溶液；S2.在搅拌的条件下，向所述混合水溶液中加入氯金酸水溶液进行反应，得到金纳米粒子；其中，反应液中各组分的浓度为：甘油5v％～80v％、抗坏血酸1wt％～10wt％、柠檬酸钠0.05wt％～0.5wt％、聚乙烯吡咯烷酮0.05wt％～0.5wt％、氯金酸0.01wt％～0.1wt％。本发明的尺寸可调的金纳米粒子的制备方法，步骤简单，可在常温常压下进行，无需复杂的装置，并且合成的金纳米粒子尺寸可控。

Description

一种尺寸可调的金纳米粒子的制备方法 技术领域
本发明涉及纳米粒子制备技术领域，具体涉及一种尺寸可调的金纳米粒子的制备方法。
背景技术
纳米材料通常是指材料的三维尺寸中至少有一个维度处在纳米尺度。纳米尺度的粒子由于具有小尺寸效应、表面效应以及量子尺寸效应等，与宏观金属粒子相比，纳米尺寸的金属粒子具有独特的热、光、电、磁和催化等性能。金属纳米颗粒的特殊性质在很大程度上取决于其大小、形状以及聚集状态。由于不同尺寸的纳米粒子呈现不同的性质，在光学、电子学、催化领域等基础科学和技术领域至关重要。其中，金纳米粒子的尺寸效应被广泛研究。不同尺寸的金纳米粒子呈现不同的颜色，其表面等离激元共振峰位置会随粒子尺寸变大而发生红移。
合成纳米结构的方法主要有两种方法：自上而下和自下而上。自上而下的方法是通过切割或者粉碎大块材料而得到小粒径的纳米粒子，通常需要大型的设备。自下而上，则是从底部开始构造，即从原子、分子或纳米粒子通过粒子间相互作用或者自组装逐步堆积而成。从化学实验室的科研而言，更多的采用自下而上的研究方法。
Turkevich-Frens法是目前最常用的制备金纳米粒子的方法，并且可以调控粒子的尺寸。该方法由Turkevich于1951年首创，并在1973年由Frens改进。该方法通过调节柠檬酸钠与氯金酸的比例调控粒子的尺寸。该方法虽然经典，但是该方法具有一定的局限性，比如：反应在沸腾的水体系中进行，需要高温 加热设备以及冷凝回流装置。因此，受制于装置的数量，纳米粒子的合成也就不能大批量进行。另外，为了确保加热实验的安全性，通常还需要人员值守，因此，为合成的便利性方面带来了一定的麻烦。此外，Brust-Schiffrin法，也是一种经典的合成金纳米粒子的方法。但是该方法制备的纳米粒子尺寸很小。其中，用到了相转移，引入了有机试剂，且需使用冰浴，操作步骤比较繁琐。操作过程中还要使用硫醇，硫醇中的巯基可强烈的吸附在金的表面，因而不利于金纳米粒子的后续应用。
发明内容
本发明要解决的技术问题是提供一种尺寸可调的金纳米粒子的制备方法，该制备方法步骤简单，可在常温常压下进行，无需复杂的装置，并且合成的金纳米粒子的尺寸可控。
为了解决上述技术问题，本发明提供了如下的技术方案：
本发明提供了一种尺寸可调的金纳米粒子的制备方法，包括以下步骤：
S1.配制溶质为甘油、抗坏血酸、柠檬酸钠和聚乙烯吡咯烷酮的混合水溶液；
S2.在搅拌的条件下，向所述混合水溶液中加入氯金酸水溶液进行反应，得到金纳米粒子；其中，反应液中各组分的浓度为：甘油5v％～80v％、抗坏血酸1wt％～10wt％、柠檬酸钠0.05wt％～0.5wt％、聚乙烯吡咯烷酮0.05wt％～0.5wt％、氯金酸0.01wt％～0.1wt％。
进一步地，步骤S1中，所述聚乙烯吡咯烷酮的分子量为5000-40000。
进一步地，步骤S1中，所述混合水溶液的配制方法为：分别将甘油、抗坏血酸、柠檬酸钠和聚乙烯吡咯烷酮配制成水溶液，再将各种水溶液混合，得到所述混合水溶液。
进一步地，步骤S2中，所述反应的条件为室温。
进一步地，步骤S2中，所述反应液中氯金酸与甘油的摩尔比为1:272～1:43580。
进一步地，步骤S2中，所述反应液中氯金酸与抗坏血酸的摩尔比为1:23～1:2338。
进一步地，步骤S2中，所述反应的时间为1～10min。
进一步地，步骤S2中，反应结束后，收集沉淀物，洗涤后得到金纳米粒子。
进一步地，步骤S2中，所述金纳米粒子呈球状，尺寸为40nm～300nm。
本发明的有益效果：
1.本发明的金纳米粒子的制备方法中，所用的试剂均为常用试剂，价格便宜，容易购买，另外所使用的试剂甘油、抗坏血酸、柠檬酸钠、聚乙烯吡咯烷酮均可用做食品添加剂，对环境无污染，对人体无伤害。
2.本发明的制备方法在常温常压下进行，所需的仪器设备简单，为常用的玻璃反应瓶、一次性巴氏滴管和移液器，不需要高压反应釜等有风险的加热装置和回流冷凝管等复杂玻璃仪器。没有仪器和设备的局限性，可以很容易地批量合成该金纳米粒子。
3.本发明的合成实验中涉及的操作均为简单操作，仅仅需要滴加，搅拌，离心等最常规的步骤。
4.反应时间：由于甘油的浓度差异，反应时间在1-10分钟不等。与很多纳米粒子动则数小时甚至一天都无法完成合成过程相比，本发明的纳米粒子耗时少，便于实际应用。
5.残留物：本实验中没有引入有机溶剂等环境不友好的试剂，反应体系也是水溶液体系，试剂均是对人体无害的绿色试剂，彰显了本发明是一种绿色环 保的纳米粒子合成方法。
6.在常见的纳米粒子中，金纳米粒子研究历史悠久，涉及较多的领域。当金纳米粒子与磁性纳米粒子结合，可用于肿瘤的靶向载药治疗。也可将表面等离激元振动峰在红外区的金纳米粒子用于癌症的热疗应用。在光谱学领域，金纳米粒子是稳定的表面增强拉曼光谱基底，可以有效的检测痕量物质及动态监测化学反应过程。在催化领域，金纳米粒子应用广泛，可用于氧还原反应、CO催化反应、燃料电池催化剂等。
附图说明
图1是本发明实施例1制备的金纳米粒子的扫描电镜图；
图2是本发明实施例2制备的金纳米粒子的扫描电镜图；
图3是本发明实施例3制备的金纳米粒子的扫描电镜图；
图4是本发明实施例1制备的金纳米粒子的紫外可见吸收光谱图；
图5是本发明实施例2制备的金纳米粒子的紫外可见吸收光谱图；
图6是本发明实施例3制备的金纳米粒子的紫外可见吸收光谱图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好地理解本发明并能予以实施，但所举实施例不作为对本发明的限定。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“及/或”包括一个或多个相关的所列项目的任意的和所有的组合。
下述实施例中所使用的实验方法如无特殊说明，均为常规方法，所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
如背景技术所述，目前经典的金纳米粒子合成方法Turkevich-Frens法和Brust-Schiffrin法均存在一定的缺陷：Turkevich-Frens法需要在沸腾的水体系中进行，需要高温加热设备以及冷凝回流装置；受制于装置的数量，纳米粒子的合成也就不能大批量进行。Brust-Schiffrin法制备的纳米粒子尺寸很小，制备过程中用到了相转移，引入了有机试剂，且需使用冰浴，操作步骤比较繁琐；操作过程中还要使用硫醇，硫醇中的巯基可强烈的吸附在金的表面，因而不利于金纳米粒子的后续应用。
为了解决金纳米粒子合成中的上述问题，发明人经过长期的研究，提出了一种新的金纳米粒子的合成方法，其具体步骤为：
S1.配制溶质为甘油、抗坏血酸、柠檬酸钠和聚乙烯吡咯烷酮的混合水溶液；
S2.在搅拌的条件下，向所述混合水溶液中加入氯金酸水溶液进行反应，得到金纳米粒子；其中，反应液中各组分的浓度为：甘油5v％～80v％、抗坏血酸1wt％～10wt％、柠檬酸钠0.05wt％～0.5wt％、聚乙烯吡咯烷酮0.05wt％～0.5wt％、氯金酸0.01wt％～0.1wt％。
与Turkevich-Frens法不同，本发明中的柠檬酸钠并不作为还原剂，而是另加了抗坏血酸作为还原剂，其在常温下即可还原氯金酸得到金纳米粒子，因此本发明的反应条件十分温和，在常温常压下即可进行，更加绿色、节能环保；所需的仪器设备也非常简单，为常用的玻璃反应瓶、一次性巴氏滴管和移液器，不需要高压反应釜等有风险的加热装置和回流冷凝管等复杂玻璃仪器；并且没有仪器和设备的局限性，可以很容易地批量合成该金纳米粒子。优选地，反应液中氯金酸与抗坏血酸的摩尔比为1:23～1:2338。
本发明中，加入的柠檬酸钠主要起到防止合成的金纳米粒子聚沉的作用。柠檬酸钠电离后产生的柠檬酸根会吸附于金纳米粒子的表面形成保护层，使得金纳米粒子的表面带负电荷，由于静电排斥作用，使得金纳米粒子能够稳定地 分散于溶液中而不会聚沉，提高了金纳米粒子的稳定性。
聚乙烯吡咯烷酮是一种水溶性的高分子化合物，其能够吸附在金纳米粒子的表面上，包围住金纳米粒子，形成一层高分子保护膜，阻止了金纳米粒子之间的直接接触，从而进一步地增加了金纳米粒子的稳定性。采用的聚乙烯吡咯烷酮的分子量优选为为5000-40000，进一步优选为10000。
此外，本发明巧妙地利用了体系粘度越大、纳米粒子生长的越慢，制备出的纳米粒子尺寸越大这一特性，向体系中加入了一定量的甘油以调节溶液的粘度，从而能够调控合成的金纳米粒子的尺寸。优选地，反应液中氯金酸与甘油的摩尔比为1:272～1:43580。
本发明中，根据反应液中甘油的浓度差异，反应时间在1-10分钟不等，耗时短，便于实际应用。反应结束后，可通过离心收集沉淀物，接着经多次洗涤、干燥后得到金纳米粒子。
本发明合成的金纳米粒子呈球状，尺寸为40nm～300nm，且分散性良好(见附图1-3)。
本发明合成的金纳米粒子应用广泛，例如与磁性纳米粒子结合，可用于肿瘤的靶向载药治疗；也可将表面等离激元振动峰在红外区的金纳米粒子用于癌症的热疗应用；在光谱学领域，金纳米粒子是稳定的表面增强拉曼光谱基底，可以有效的检测痕量物质及动态监测化学反应过程；在催化领域，可用于氧还原反应、CO催化反应、燃料电池催化剂等。
实施例1
一种尺寸可调的金纳米粒子合成方法，其步骤如下：
1.称取2.112g的抗坏血酸(国药)配成20mL水溶液。
2.将1g氯金酸(国药)配成100mL水溶液。
3.称取1g分子量的10000聚乙烯吡咯烷酮(Sigma-Aldrich)配成100ml 水溶液。
4.称取1g柠檬酸钠配成100ml水溶液。
5.将1mL甘油(国药)和9mL超纯水加入反应瓶中，加入2ml抗坏血酸水溶液，搅拌均匀之后各加1ml柠檬酸钠和聚乙烯吡咯烷酮水溶液。边搅边加入500μL氯金酸水溶液，直至反应完全。离心洗涤后进行扫描电子显微镜表征，结果如图1所示。从图中可以看出，本实施例成功地得到了球状金纳米粒子，尺寸约为60nm。
实施例2
一种尺寸可调的金纳米粒子合成方法，其步骤如下：
1.称取2.112g的抗坏血酸(国药)配成20mL水溶液。
2.将1g氯金酸(国药)配成100mL水溶液。
3.称取1g分子量10000的聚乙烯吡咯烷酮(Sigma-Aldrich)配成100ml水溶液。
4.称取1g柠檬酸钠配成100ml水溶液。
5.将5mL甘油(国药)和5mL超纯水加入反应瓶中，加入2ml抗坏血酸水溶液，搅拌均匀之后各加1ml柠檬酸钠和聚乙烯吡咯烷酮水溶液。边搅边加入500μL氯金酸水溶液，直至反应完全。离心洗涤后进行扫描电子显微镜表征，结果如图2所示。从图中可以看出，本实施例成功地得到了球状金纳米粒子，尺寸约为200nm。
实施例3
一种尺寸可调的金纳米粒子合成方法，其步骤如下：
1.称取2.112g的抗坏血酸(国药)配成20mL水溶液。
2.将1g氯金酸(国药)配成100mL水溶液。
3.称取1g分子质量为1000的聚乙烯吡咯烷酮(Sigma-Aldrich)配成100ml水溶液。
4.称取1g柠檬酸钠配成100ml水溶液。
5.将8mL甘油(国药)和2mL超纯水加入反应瓶中，加入2ml抗坏血酸水溶液，搅拌均匀之后各加1ml柠檬酸钠和聚乙烯吡咯烷酮水溶液。边搅边加入500μL氯金酸水溶液，直至反应完全。离心洗涤后进行扫描电子显微镜表征，结果如图3所示。从图中可以看出，本实施例成功地得到了球状金纳米粒子，尺寸约为245nm。
以上所述实施例仅是为充分说明本发明而所举的较佳的实施例，本发明的保护范围不限于此。本技术领域的技术人员在本发明基础上所作的等同替代或变换，均在本发明的保护范围之内。本发明的保护范围以权利要求书为准。

Claims (9)

  1. 一种尺寸可调的金纳米粒子的制备方法，其特征在于，包括以下步骤：
    S1.配制溶质为甘油、抗坏血酸、柠檬酸钠和聚乙烯吡咯烷酮的混合水溶液；
    S2.在搅拌的条件下，向所述混合水溶液中加入氯金酸水溶液进行反应，得到金纳米粒子；其中，反应液中各组分的浓度为：甘油5v％～80v％、抗坏血酸1wt％～10wt％、柠檬酸钠0.05wt％～0.5wt％、聚乙烯吡咯烷酮0.05wt％～0.5wt％、氯金酸0.01wt％～0.1wt％。
  2. 根据权利要求1所述的一种尺寸可调的金纳米粒子的制备方法，其特征在于，步骤S1中，所述聚乙烯吡咯烷酮的分子量为5000-40000。
  3. 根据权利要求1所述的一种尺寸可调的金纳米粒子的制备方法，其特征在于，步骤S1中，所述混合水溶液的配制方法为：分别将甘油、抗坏血酸、柠檬酸钠和聚乙烯吡咯烷酮配制成水溶液，再将各种水溶液混合，得到所述混合水溶液。
  4. 根据权利要求1所述的一种尺寸可调的金纳米粒子的制备方法，其特征在于，步骤S2中，所述反应的条件为室温。
  5. 根据权利要求1所述的一种尺寸可调的金纳米粒子的制备方法，其特征在于，步骤S2中，所述反应液中氯金酸与甘油的摩尔比为1:272～1:43580。
  6. 根据权利要求1所述的一种尺寸可调的金纳米粒子的制备方法，其特征在于，步骤S2中，所述反应液中氯金酸与抗坏血酸的摩尔比为1:23～1:2338。
  7. 根据权利要求1所述的一种尺寸可调的金纳米粒子的制备方法，其特征在于，步骤S2中，所述反应的时间为1～10min。
  8. 根据权利要求1所述的一种尺寸可调的金纳米粒子的制备方法，其特征在于，步骤S2中，反应结束后，收集沉淀物，洗涤后得到金纳米粒子。
  9. 根据权利要求1所述的一种尺寸可调的金纳米粒子的制备方法，其特征在于，步骤S2中，所述金纳米粒子呈球状，尺寸为40nm～300nm。
PCT/CN2020/126905 2020-07-23 2020-11-06 一种尺寸可调的金纳米粒子的制备方法 WO2022016741A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010719115.1 2020-07-23
CN202010719115.1A CN111702186B (zh) 2020-07-23 2020-07-23 一种尺寸可调的金纳米粒子的制备方法

Publications (1)

Publication Number Publication Date
WO2022016741A1 true WO2022016741A1 (zh) 2022-01-27

Family

ID=72547597

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/126905 WO2022016741A1 (zh) 2020-07-23 2020-11-06 一种尺寸可调的金纳米粒子的制备方法

Country Status (2)

Country Link
CN (1) CN111702186B (zh)
WO (1) WO2022016741A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115060904A (zh) * 2022-08-16 2022-09-16 山东康华生物医疗科技股份有限公司 一种乙肝表面抗原检测试剂盒用胶体金溶液的制备方法及试剂条、试剂盒

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111702186B (zh) * 2020-07-23 2023-03-24 苏州大学 一种尺寸可调的金纳米粒子的制备方法
CN112326962B (zh) * 2020-11-03 2021-10-12 山西康健恩生物科技有限公司 一种新型冠状病毒抗原胶体金快速诊断试剂盒及其制备方法
CN116786834B (zh) * 2023-06-21 2024-03-22 江苏默乐生物科技股份有限公司 一种大粒径胶体金及其制备方法和应用

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105108137A (zh) * 2015-09-24 2015-12-02 厦门大学 一种强过氧化氢酶活性的纳米颗粒的制备方法
CN105170997A (zh) * 2015-10-13 2015-12-23 东南大学 双还原剂纳米金量子点的室温快速合成方法
CN106112006A (zh) * 2016-07-22 2016-11-16 国家纳米科学中心 一种金纳米粒子水溶液及其制备方法和应用
CN107511479A (zh) * 2017-09-08 2017-12-26 厦门大学 一种超薄壳层隔绝大粒径金纳米粒子的合成方法
CN107916595A (zh) * 2017-11-17 2018-04-17 天津科技大学 一种抑菌纸基材料及其制备方法
CN110280780A (zh) * 2019-07-28 2019-09-27 长春黄金研究院烟台贵金属材料研究所有限公司 一种基于溶金的纳米金溶胶制备方法
CN110405223A (zh) * 2019-08-12 2019-11-05 北京科技大学 一种高纯度的尺寸可控纳米金颗粒的制备方法
CN111702186A (zh) * 2020-07-23 2020-09-25 苏州大学 一种尺寸可调的金纳米粒子的制备方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008105456A1 (ja) * 2007-02-27 2008-09-04 Mitsubishi Materials Corporation 金属ナノ粒子分散液及びその製造方法並びに金属ナノ粒子の合成方法
DE102011085642A1 (de) * 2011-11-03 2013-05-08 Bayer Materialscience Aktiengesellschaft Verfahren zur Herstellung einer Metallnanopartikeldispersion, Metallnanopartikeldispersion sowie deren Verwendung

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105108137A (zh) * 2015-09-24 2015-12-02 厦门大学 一种强过氧化氢酶活性的纳米颗粒的制备方法
CN105170997A (zh) * 2015-10-13 2015-12-23 东南大学 双还原剂纳米金量子点的室温快速合成方法
CN106112006A (zh) * 2016-07-22 2016-11-16 国家纳米科学中心 一种金纳米粒子水溶液及其制备方法和应用
CN107511479A (zh) * 2017-09-08 2017-12-26 厦门大学 一种超薄壳层隔绝大粒径金纳米粒子的合成方法
CN107916595A (zh) * 2017-11-17 2018-04-17 天津科技大学 一种抑菌纸基材料及其制备方法
CN110280780A (zh) * 2019-07-28 2019-09-27 长春黄金研究院烟台贵金属材料研究所有限公司 一种基于溶金的纳米金溶胶制备方法
CN110405223A (zh) * 2019-08-12 2019-11-05 北京科技大学 一种高纯度的尺寸可控纳米金颗粒的制备方法
CN111702186A (zh) * 2020-07-23 2020-09-25 苏州大学 一种尺寸可调的金纳米粒子的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
NALAWADE PRADNYA, MUKHERJEE TULSI, KAPOOR SUDHIR: "Green Synthesis of Gold Nanoparticles Using Glycerol as a Reducing Agent", ADVANCES IN NANOPARTICLES, SCIENTIFIC RESEARCH PUBLISHING, INC., UNITED STATES, vol. 02, no. 02, 1 January 2013 (2013-01-01), United States , pages 78 - 86, XP055888332, ISSN: 2169-0510, DOI: 10.4236/anp.2013.22014 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115060904A (zh) * 2022-08-16 2022-09-16 山东康华生物医疗科技股份有限公司 一种乙肝表面抗原检测试剂盒用胶体金溶液的制备方法及试剂条、试剂盒

Also Published As

Publication number Publication date
CN111702186A (zh) 2020-09-25
CN111702186B (zh) 2023-03-24

Similar Documents

Publication Publication Date Title
WO2022016741A1 (zh) 一种尺寸可调的金纳米粒子的制备方法
Kumar et al. Metallic nanoparticle: a review
Yamamoto et al. Size-controlled synthesis of monodispersed silver nanoparticles capped by long-chain alkyl carboxylates from silver carboxylate and tertiary amine
Pol et al. Synthesis of europium oxide nanorods by ultrasound irradiation
Zhou et al. Minute synthesis of extremely stable gold nanoparticles
Liang et al. Controlled synthesis of uniform silver nanospheres
Hu et al. Microwave-assisted rapid facile “green” synthesis of uniform silver nanoparticles: self-assembly into multilayered films and their optical properties
Zhu et al. A simple one-pot self-assembly route to nanoporous and monodispersed Fe3O4 particles with oriented attachment structure and magnetic property
Xia et al. Synthesis of monodisperse quasi-spherical gold nanoparticles in water via silver (I)-assisted citrate reduction
Zhou et al. Controlled synthesis of high-quality PbS star-shaped dendrites, multipods, truncated nanocubes, and nanocubes and their shape evolution process
Xie et al. Synthesis of single-crystalline gold nanoplates in aqueous solutions through biomineralization by serum albumin protein
Lin et al. A simple synthesis method for gold nano-and microplate fabrication using a tree-type multiple-amine head surfactant
Guo et al. Synthesis and characterization of carbon sphere-silica core–shell structure and hollow silica spheres
Kundu et al. Size-selective synthesis and catalytic application of polyelectrolyte encapsulated gold nanoparticles using microwave irradiation
Mandal Goswami Synthesis of micelles guided magnetite (Fe3O4) hollow spheres and their application for AC magnetic field responsive drug release
CN106587078A (zh) 一种介孔二氧化硅纳米粒子的制备方法
TWI639426B (zh) 一種含有配位子鍵結的金奈米團簇的溶液之製備方法
CN104591275B (zh) 水介质分散铈锆氧化物纳米材料的合成方法
Yougen et al. Preparation of monodisperse polystyrene/silver composite microspheres and their catalytic properties
Mahyari et al. Synthesis of gold nanoflowers using deep eutectic solvent with high surface enhanced Raman scattering properties
Chen et al. Self-assembly of gold nanoparticles to silver microspheres as highly efficient 3D SERS substrates
CN105832699A (zh) 一种Fe3O4@SiO2蛋黄-蛋壳结构中空复合微球的制备方法及应用
Li et al. A facile construction of Au nanoparticles stabilized by thermo-responsive polymer-tethered carbon dots for enhanced catalytic performance
Ke et al. Synthesis and characterization of core-shell mesoporous silica nanoparticles with various shell thickness as indomethacin carriers: In vitro and in vivo evaluation
Shiau et al. The characteristics and mechanisms of Au nanoparticles processed by functional centrifugal procedures

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20946465

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20946465

Country of ref document: EP

Kind code of ref document: A1