Paper-based gold nanoparticle synthesis method, paper-based gold nanoparticle device and application
By synthesizing gold nanoparticles in situ on the porous fiber paper substrate, dispersing and fixing AuNPs with the three-dimensional network structure of paper fibers, the problem of unstable catalytic performance aggregation in solution is solved, and its efficient application in biocatalytic and environmental detection is achieved.
Patent Information
- Application Number
- CN202411802329.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-09
- Publication Date
- 2025-04-01
- Estimated Expiration
- 2044-12-09
AI Technical Summary
Gold nanoparticles (AuNPs) are prone to aggregation in solution, resulting in unstable catalytic performance and limiting their effectiveness in practical applications.
By synthesizing gold nanoparticles in situ on a porous fiber paper substrate, AuNPs are dispersed and fixed using the three-dimensional mesh structure of the paper fibers to prevent the aggregation of particles.
The uniform dispersion and long-lasting stability of AuNPs are achieved, which improves the catalytic performance of its catalase-like body, enhances the anti-interference ability, simplifies the preparation process and reduces costs.
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Figure CN119733844A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of nanomaterials and biocatalysis, in particular to a method for synthesizing paper-based nanoparticles, a paper-based nanoparticle device and an application thereof. By utilizing the three-dimensional network structure of paper fibers to disperse and fix gold nanoparticles AuNPs, the aggregation of particles can be prevented, so that the gold nanoparticles exhibit better anti-interference ability in a complex environment and maintain their efficient catalytic activity. Background Art
[0002] Gold nanoparticles (AuNPs), as an important nanomaterial, have been widely used in catalysis, biosensing, medical imaging and drug delivery due to their excellent physical and chemical properties. In particular, in the field of catalysis, AuNPs exhibit unique enzyme-like catalytic properties, such as catalase-like activity, which makes them ideal candidate materials for environmental pollutant detection and biocatalysis research.
[0003] However, the catalytic performance of AuNPs depends largely on their surface activity and dispersibility. When AuNPs are at the nanoscale, their surface area is large and can provide more active sites, thus showing higher catalytic efficiency. However, due to the strong van der Waals forces and surface energy between nanoparticles, they tend to aggregate in solution to form larger particles or clusters. This aggregation phenomenon significantly reduces the surface area of AuNPs, thereby weakening their catalytic performance. In addition, AuNPs are also easily interfered by solution pH, ionic strength and other chemicals in practical applications, which further affects their catalytic effect and stability.
[0004] In order to overcome the above problems, researchers have proposed a variety of methods to stabilize AuNPs and improve their catalytic performance. For example, by modifying the surface of AuNPs with organic molecules or polymers, their aggregation can be prevented to a certain extent. However, these methods often have the disadvantages of complex processes, high costs, and the possibility of affecting the catalytic activity of AuNPs. Therefore, finding a simple, effective and low-cost method to stabilize AuNPs to maintain its excellent catalytic performance has become a hot topic in current research.
[0005] In order to solve the problem of decreased catalytic performance caused by the instability of gold nanoparticles, the present invention proposes a new strategy of in-situ synthesis of AuNPs on a porous fiber paper substrate. The natural porous structure of paper fibers can effectively disperse and fix AuNPs, prevent the aggregation of particles, and maintain their efficient catalytic activity. In addition, the three-dimensional network structure of paper fibers provides additional protection for AuNPs, enabling them to exhibit better anti-interference ability in complex environments. This innovative design not only simplifies the preparation process of AuNPs and reduces costs, but also significantly enhances its practical application potential in fields such as biocatalysis and environmental testing. Summary of the invention
[0006] In view of the deficiencies in the prior art, the present invention provides a method for synthesizing paper-based nanoparticles, a paper-based nanoparticle device and an application thereof. By utilizing the three-dimensional network structure of paper fibers to disperse and fix gold nanoparticles AuNPs, the aggregation of particles can be prevented, so that the gold nanoparticles exhibit better anti-interference ability in complex environments and maintain their efficient catalytic activity.
[0007] The technical solution of the present invention is as follows: A method for synthesizing paper-based nanoparticles, characterized in that it comprises the following steps: Step 1, cleaning and activating the paper so as to maintain and strengthen the three-dimensional mesh fiber structure of the paper; Step 2, soaking the cleaned and activated paper in a solution of chloroauric acid, a gold precursor, so that the chloroauric acid molecules are fully adsorbed into the three-dimensional network fiber structure of the paper itself; Step 3, using a reducing agent to reduce the chloroauric acid molecules in the three-dimensional mesh fiber structure into gold nanoparticles to achieve in situ synthesis of AuNPs; Step 4, drying the paper with in situ synthesized AuNPs and storing it in a refrigerator.
[0008] The cleaning process in step 1 includes removing impurities and / or contaminants on the surface of the paper using deionized water and / or ethanol solution.
[0009] The activation treatment in step 1 includes activating the paper fibers by means of ultraviolet light irradiation, thereby enhancing the interaction between the paper fibers and the gold precursor, thereby improving the adsorption capacity of the paper fibers for the gold precursor.
[0010] Step 2 includes using a rotary oscillation device to perform a rotary oscillation treatment on the chloroauric acid solution, and then washing with deionized water and / or ethanol solution to remove the chloroauric acid molecules that are not adsorbed by the paper fibers.
[0011] Step 3 includes using trisodium citrate as a reducing agent, and using a rotating oscillation device to perform a rotating oscillation treatment on the trisodium citrate solution soaked with paper in a heated state, and then rinsing with deionized water and / or ethanol solution.
[0012] The concentration of the chloroauric acid solution is 10 nanomolar.
[0013] The concentration of the trisodium citrate solution is 1 wt %.
[0014] A paper-based nanoparticle device is made by the above-mentioned paper-based nanoparticle synthesis method, characterized in that it includes cutting the paper with in-situ synthesized AuNPs stored in refrigeration into devices of different shapes or sizes.
[0015] An application of a paper-based nanoparticle device, characterized in that it includes applying the above-mentioned paper-based nanoparticle device to environmental pollutant detection, medical diagnosis and / or industrial catalysis.
[0016] The technical effects of the present invention are as follows: The present invention provides a method for synthesizing paper-based nanoparticles, a paper-based nanoparticle device and an application thereof, which can solve the problem that AuNPs are easily aggregated in a solution, resulting in a decrease in catalytic performance, and improve the catalytic performance of catalase-like enzymes by enhancing their stability and anti-interference ability. The present invention utilizes the natural porous structure of paper fibers as a carrier, and through a simple and efficient in-situ synthesis technology, AuNPs are stably loaded on a paper substrate, thereby achieving uniform dispersion and long-term stability of the nanoparticles.
[0017] Compared with the prior art, the present invention has the following advantages: 1. Simple process and economical and efficient: The present invention simplifies the preparation process of AuNPs by optimizing the synthesis process. The entire synthesis process does not require complicated surface modification or other protection steps, and only uses the natural porous structure of paper fibers to achieve stable loading and dispersion of nanoparticles, greatly reducing production costs.
[0018] 2. Significantly improved stability: By loading AuNPs on a paper substrate, the nanoparticles are effectively protected by a physical barrier, avoiding aggregation and growth between particles, thereby maintaining their unique nanoscale properties. At the same time, the network structure of paper fibers provides AuNPs with a larger specific surface area, making them more active in the catalytic process, especially the catalytic activity of catalase-like enzymes has been significantly improved.
[0019] 3. Process repeatability and scalability: This method is simple and easy to implement, with high process repeatability, and is suitable for large-scale production. At the same time, the selection of filter paper materials and processing conditions can be adjusted according to specific applications, thereby expanding to the preparation of other types of metal nanoparticles.
[0020] 4. Strong anti-interference ability: Unlike traditional free AuNPs, AuNPs loaded on paper substrates show stronger resistance to common factors in the environment such as pH fluctuations and ion interference, which makes their performance in complex sample detection more reliable and stable.
[0021] 5. Wide application potential: The technical solution of the present invention is not only applicable to the preparation of gold nanoparticles, but can also be extended to the synthesis of other metal nanoparticles, such as silver, copper, platinum, etc., so as to play a role in a wider range of fields, including but not limited to catalyst preparation, sensor development and medical diagnosis.
[0022] In summary, the present invention proposes a method for synthesizing AuNPs based on paper fiber structure, which achieves efficient stabilization of gold nanoparticles and enhancement of catalytic performance by utilizing the natural advantages of the paper substrate, and has important scientific research value and industrial application prospects. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1 It is a schematic diagram of a process for implementing a method for synthesizing paper-based nanoparticles of the present invention. Figure 1 The symbols are explained as follows: 1-filter paper; 2-chloroauric acid solution; 3-filter paper after pretreatment; 4-trisodium citrate solution; 5-gold nanoparticles based on paper fiber structure.
[0024] Figure 2 This is a real picture of AuNPs based on paper fiber structure.
[0025] Figure 3 Scanning electron microscopy image of AuNPs based on paper fiber structure. DETAILED DESCRIPTION
[0026] Below is the attached figure ( Figure 1-Figure 3 ) and examples illustrate the present invention.
[0027] Figure 1 It is a schematic diagram of a process for implementing a method for synthesizing paper-based nanoparticles of the present invention. Figure 2 This is a real picture of AuNPs based on paper fiber structure. Figure 3 This is a scanning electron micrograph of AuNPs based on paper fiber structure. Figures 1 to 3 As shown, a method for synthesizing gold nanoparticles from paper includes the following steps: step 1, cleaning and activating the paper so that the three-dimensional network fiber structure of the paper itself is maintained and strengthened; step 2, soaking the cleaned and activated paper in a solution of chloroauric acid, a gold precursor, so that the chloroauric acid molecules are fully adsorbed into the three-dimensional network fiber structure of the paper itself; step 3, using a reducing agent to reduce the chloroauric acid molecules in the three-dimensional network fiber structure into gold nanoparticles to achieve in-situ synthesis of AuNPs; step 4, drying the paper on which AuNPs are synthesized in situ and storing it in a refrigerator.
[0028] The cleaning treatment in step 1 includes removing impurities and / or pollutants on the surface of the paper using deionized water and / or ethanol solution. The activation treatment in step 1 includes activating the paper fibers by ultraviolet light irradiation to enhance the interaction between the paper fibers and the gold precursor, thereby improving the adsorption capacity of the paper fibers to the gold precursor.
[0029] Step 2 includes using a rotary oscillation device to perform a rotary oscillation treatment on the chloroauric acid solution, and then washing with deionized water and / or ethanol solution to remove the chloroauric acid molecules not adsorbed by the paper fibers. Step 3 includes using trisodium citrate as a reducing agent, and using a rotary oscillation device to perform a rotary oscillation treatment on the trisodium citrate solution soaked with paper in a heated state, and then washing with deionized water and / or ethanol solution.
[0030] The concentration of the chloroauric acid solution is 10 nanomolar. The concentration of the trisodium citrate solution is 1 wt%.
[0031] A paper-based nanoparticle device is manufactured by the paper-based nanoparticle synthesis method, comprising cutting refrigerated paper for in-situ synthesis of AuNPs into devices of different shapes or sizes.
[0032] An application of a paper-based nanoparticle device comprises applying the paper-based nanoparticle device to environmental pollutant detection, medical diagnosis and / or industrial catalysis.
[0033] The present invention relates to the technical field of nanomaterials and biocatalysis, and in particular to a novel method for in-situ synthesis of gold nanoparticles (AuNPs) on a porous fiber paper substrate, and the application of the AuNPs prepared thereby in biocatalysis and environmental detection. Gold nanoparticles have a wide range of application prospects in catalysis, biosensing and medical diagnosis due to their unique physical and chemical properties. However, since gold nanoparticles are easily aggregated in a solution, their catalytic performance is unstable, which limits their effect in practical applications.
[0034] The present invention directly synthesizes and loads AuNPs on a paper substrate by utilizing the natural porous structure of paper fibers, thereby effectively avoiding the problem of particle aggregation. The three-dimensional network structure of paper fibers can not only stably load nanoparticles, but also provide additional protection, so that AuNPs show better anti-interference ability and stability in complex environments. The AuNPs prepared by the present invention show excellent catalase-like catalytic performance, and are particularly suitable for practical applications in the fields of environmental pollutant detection, medical diagnosis, and industrial catalysis.
[0035] The present invention provides an innovative method for synthesizing gold nanoparticles (AuNPs) based on porous fiber paper substrates, aiming to solve the problem of AuNPs easily aggregating in solution, resulting in decreased catalytic performance, and improve its catalase-like catalytic performance by enhancing its stability and anti-interference ability. This method uses the natural porous structure of paper fibers as a carrier, and through a simple and efficient in-situ synthesis technology, AuNPs are stably loaded on the paper substrate, thereby achieving uniform dispersion and long-term stability of the nanoparticles.
[0036] Specifically, the technical solution of the present invention includes the following steps: 1. Pretreatment of paper substrate: Filter paper with a diameter of 8 mm was selected as the substrate material and pretreated. First, the surface was cleaned and activated. The cleaning step was carried out using deionized water and ethanol solution to remove impurities and contaminants that may exist on the surface. Then, the paper fibers were activated by ultraviolet light irradiation to enhance their interaction with the gold precursor (chloroauric acid), thereby improving the adsorption capacity of the gold precursor. This pretreatment step not only ensures the uniformity of the subsequent synthesis, but also enhances the adhesion stability of AuNPs on the paper substrate.
[0037] 2. In-situ synthesis of gold nanoparticles - Step 1: Soak the pretreated filter paper in chloroauric acid solution (0.5 ml, 10 nanomolar concentration), and then oscillate at a speed of 90 rad / s for 20 minutes on a rotary oscillator. The purpose of this step is to allow the chloroauric acid molecules to be fully adsorbed into the pores of the filter paper, thereby laying the foundation for the subsequent synthesis of nanoparticles. After the oscillation, rinse twice with deionized water and ethanol solution respectively to remove unadsorbed chloroauric acid molecules and other impurities.
[0038] 3. In-situ synthesis of gold nanoparticles - Step 2: In-situ synthesis of AuNPs on the filter paper treated in the previous step. The specific operation steps include soaking the rinsed filter paper in the filtered trisodium citrate solution (0.5 ml, 1% concentration), followed by rotation and shaking at 80°C for 30 minutes. In this process, trisodium citrate acts as a reducing agent to reduce the chloroauric acid adsorbed in the pores of the filter paper into gold nanoparticles. In this process, gold nanoparticles are formed directly on the paper fibers and firmly attached to the paper substrate. Unlike traditional chemical reduction methods, the present invention does not require the addition of additional surfactants or protective agents, and only utilizes the structural characteristics of paper fibers to achieve stable dispersion of AuNPs. After the shaking is completed, the filter paper is rinsed twice with deionized water and ethanol solution respectively to remove excess chemicals.
[0039] 4. Post-processing and application: The synthesized AuNPs-loaded filter paper is further stabilized by drying and refrigerated storage. The filter paper after these processing steps has excellent stability and catalytic performance, and is particularly suitable for application fields such as environmental testing, biosensing and industrial catalysis. Due to the flexibility and cuttability of the paper substrate, these AuNPs-loaded filter papers can also be further processed into devices of different shapes or sizes according to specific application requirements.
[0040] The present invention discloses a synthesis of AuNPs nanoparticles based on a paper fiber pore structure and a catalytic application with enhanced stability, taking the chemical reaction of catalyzing hydrogen peroxide as an example, comprising the following steps: 1. At the same time, take another centrifuge tube and add the following: 80 μL, 10 mM 3,3′,5,5′-tetramethylbenzidine (TMB) solution, 100 μL, 0.1% hydrogen peroxide (H2O2), mix and incubate for 10 minutes.
[0041] 2. Then add a piece of synthesized paper-based AuNPs into step 1.
[0042] 3. The solution in step 2 was observed to change from colorless to blue, proving that the paper-based AuNPs had good stability and catalytic performance.
[0043] 4. Explanation of chemical reaction mechanism: Paper-based AuNPs were able to catalyze the oxidation of TMB to its oxidized form TMBox in the presence of H2O2, due to the peroxidase-like catalytic activity of AuNPs.
[0044] The specific mechanism can be explained in the following steps: a. Surface active sites: AuNPs have highly active uncoordinated gold atoms on their surface, which can adsorb and activate hydrogen peroxide molecules. The nanoscale size and high specific surface area of AuNPs make their surface active sites more abundant, thereby enhancing the catalytic efficiency.
[0045] b. Dissociation of H2O2: On the surface of AuNPs, H2O2 can be dissociated into active oxygen species (such as hydroxyl radical OH• and peroxyl radical HO2•) through the catalytic action of the AuNPs surface. These active oxygen species are strong oxidants that can further trigger oxidation reactions.
[0046] c. Oxidation of TMB: Under the action of these reactive oxygen species, the TMB molecule is oxidized to form a blue oxidation product, TMBox. Specifically, the amine group (–NH2) in the TMB molecule is oxidized to form an amine radical, which is then further oxidized to finally generate a blue oxidized TMBox.
[0047] Finally, it should be noted that the above is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for those skilled in the art to modify the technical solutions described in the aforementioned embodiments or to make equivalent replacements for some of the technical features therein.
[0048] The contents not described in detail in the specification of the present invention belong to the prior art known to the professional and technical personnel in the field. It is pointed out here that the above description helps those skilled in the art to understand the invention, but does not limit the protection scope of the invention. Any equivalent replacement, modification and / or simplification of the above description without departing from the essence of the invention falls within the protection scope of the invention.
Claims
1. A method for synthesizing paper-based nanoparticles, characterized in that: The following steps are involved: Step 1, cleaning and activating the paper so as to maintain and strengthen the three-dimensional mesh fiber structure of the paper; Step 2, soaking the cleaned and activated paper in a solution of chloroauric acid, a gold precursor, so that the chloroauric acid molecules are fully adsorbed into the three-dimensional network fiber structure of the paper itself; Step 3, using a reducing agent to reduce the chloroauric acid molecules in the three-dimensional mesh fiber structure into gold nanoparticles to achieve in situ synthesis of AuNPs; Step 4, drying the paper with in situ synthesized AuNPs and storing it in a refrigerator.
2. The method for synthesizing paper-based nanoparticles according to claim 1, characterized in that: The cleaning process in step 1 includes removing impurities and / or contaminants on the surface of the paper using deionized water and / or ethanol solution.
3. The method for synthesizing paper-based nanoparticles according to claim 1, characterized in that: The activation treatment in step 1 includes activating the paper fibers by means of ultraviolet light irradiation, thereby enhancing the interaction between the paper fibers and the gold precursor, thereby improving the adsorption capacity of the paper fibers for the gold precursor.
4. The method for synthesizing paper-based nanoparticles according to claim 1, characterized in that: Step 2 includes using a rotary oscillation device to perform a rotary oscillation treatment on the chloroauric acid solution, and then washing with deionized water and / or ethanol solution to remove the chloroauric acid molecules that are not adsorbed by the paper fibers.
5. The method for synthesizing paper-based nanoparticles according to claim 1, characterized in that: Step 3 includes using trisodium citrate as a reducing agent, and using a rotating oscillation device to perform a rotating oscillation treatment on the trisodium citrate solution soaked with paper in a heated state, and then rinsing with deionized water and / or ethanol solution.
6. The method for synthesizing paper-based nanoparticles according to claim 1, characterized in that: The concentration of the chloroauric acid solution is 10 nanomolar.
7. The method for synthesizing paper-based nanoparticles according to claim 5, characterized in that: The concentration of the trisodium citrate solution is 1 wt %.
8. A paper-based nanoparticle device, made by the paper-based nanoparticle synthesis method according to any one of claims 1 to 7, characterized in that: This involves cutting paper containing in situ synthesized AuNPs stored in a refrigerator into devices of different shapes or sizes.
9. An application of a paper-based nanoparticle device, characterized in that: It includes applying the paper-based nanoparticle device described in claim 8 to environmental pollutant detection, medical diagnosis and / or industrial catalysis.
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