Nanorestricted enhanced biomass-based room temperature phosphorescent material, preparation method and application thereof
Patent Information
- Application Number
- CN202610723081.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-05-25
- Publication Date
- 2026-08-21
AI Technical Summary
[0004]本发明的目的是提供纳米限域增强生物质基室温磷光材料的制备方法，解决了现有水相RTP材料难以满足多样化应用需求（防伪、信息加密）的问题
1）本发明采用水热碱煮的方法，这种方法简单且可重复性高。通过精确控制反应条件，可以确保制备过程的稳定性和可靠性。
Smart Images
Figure CN122609224A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of biomacromolecule-based functional materials technology, and relates to nano-confined enhanced biomass-based room temperature phosphorescent materials. This invention also relates to the preparation method and application of nano-confined enhanced biomass-based room temperature phosphorescent materials. Background Technology
[0002] Room-temperature phosphorescent materials possess unique characteristics such as large Stokes shifts, long-lived triplet excited states, and effective elimination of self-absorption and background fluorescence. After the excitation source is removed, room-temperature phosphorescent materials typically exhibit lifetimes ranging from a few seconds to several hours. This unique property promises wide applications in information security, optoelectronic devices, sensing, and high-sensitivity bioimaging. Luminescent nanomaterials, represented by carbon dots, have attracted increasing attention in the fields of biology, optoelectronics, and chemistry due to their good water solubility, high photostability, low toxicity, and good biocompatibility.
[0003] In existing technologies, to achieve this goal, Wang et al. from Beijing University of Chemical Technology used the confined space of layered double hydroxides (LDH) to induce structural rearrangement of terephthalic acid (TPA) with crystalline room-temperature phosphorescence (RTP) properties, forming a metastable supramolecular assembly (LSA) with aqueous RTP properties. This is a new approach to constructing aqueous RTP supramolecular materials. LDH, acting as an energy trap, overcomes the energy barrier of the ordered assembly of TPA molecules, enhances intermolecular forces, and provides a prerequisite for the stable existence of the metastable array in an aqueous environment. After the occupied groups of TPA molecules are released, the interaction sites between TPA molecules and water molecules are increased, activating aqueous RTP emission. This strategy has good versatility and provides a new idea for the development of aqueous RTP supramolecular materials. (Angewandte Chemie-International Edition 2024, 63(35):e202409162) Despite some progress, research on green-source room-temperature phosphorescent materials remains limited, especially for biomass-based materials that exhibit RTP response, which require further investigation. Therefore, it is necessary to explore novel sources of green room-temperature phosphorescent materials for the manufacture of functional phosphorescent materials to expand their functions and applications, achieve high added value and functionalization, and thus play a role in applications such as information security and advanced anti-counterfeiting. Summary of the Invention
[0004] The purpose of this invention is to provide a method for preparing nano-confined enhanced biomass-based room temperature phosphorescent materials, which solves the problem that existing aqueous RTP materials cannot meet diverse application requirements (anti-counterfeiting, information encryption).
[0005] A second objective of this invention is to provide nano-confined enhanced biomass-based room-temperature phosphorescent materials.
[0006] The third objective of this invention is to provide the application of nano-confined enhanced biomass-based room temperature phosphorescent materials in anti-counterfeiting and information encryption.
[0007] The first technical solution adopted in this invention is a method for preparing nano-confined enhanced biomass-based room temperature phosphorescent materials, which specifically includes the following steps: Step 1: Add white skin powder to deionized water, adjust the pH of the system with sodium hydroxide solution, stir magnetically under heating conditions, and after cooling to room temperature, centrifuge to obtain the supernatant, which is the collagen hydrolysate solution. Step 2: Under stirring conditions, add two-dimensional layered nanosheets to the collagen hydrolysate solution obtained in Step 1 and stir to obtain a transparent solution; Step 3: Naturally dry the transparent solution obtained in Step 2 to obtain a light yellow solid, which can be ground to obtain a two-dimensional layered nano-confined induced enhanced biomass-based room temperature phosphorescent material.
[0008] The first technical solution of this invention is further characterized by: In step 1, the pH of the system is adjusted to 10.0-13.0 using sodium hydroxide solution.
[0009] In step 1, the heating temperature is 45-60℃.
[0010] In step 1, the stirring time is 4 to 6 hours.
[0011] In step 2, the two-dimensional layered nanosheets are any one of lithium diatomite nanosheets, layered zirconium phosphate nanosheets, or layered bimetallic hydroxide nanosheets.
[0012] In step 2, the mass ratio of solid content in the two-dimensional layered nanosheets and collagen hydrolysate is 1-5:400.
[0013] In step 2, the stirring time is 20-60 minutes.
[0014] The second technical solution adopted in this invention is a nano-confined enhanced biomass-based room temperature phosphorescent material, which is prepared by the above-mentioned preparation method of nano-confined enhanced biomass-based room temperature phosphorescent material.
[0015] The third technical solution adopted in this invention is the application of nano-confined enhanced biomass-based room temperature phosphorescent materials in anti-counterfeiting and information encryption.
[0016] The beneficial effects of this invention are as follows: 1) This invention employs a hydrothermal alkaline boiling method, which is simple and highly reproducible. By precisely controlling the reaction conditions, the stability and reliability of the preparation process can be ensured.
[0017] 2) The raw materials used in this invention are safe, non-toxic, and biodegradable, meeting environmental protection requirements. Furthermore, the organic phosphorescent materials prepared from these raw materials have not been previously investigated. 3) This invention uses collagen hydrolysate and two-dimensional nanosheets as raw materials. It only requires common laboratory instruments for preparation and does not require special equipment. In addition, its process is simple and easy to operate. Attached Figure Description
[0018] Figure 1 This is a TEM image of the phosphorescent material prepared in Example 2 of the preparation method of the nano-confined enhanced biomass-based room temperature phosphorescent material of the present invention; Figure 2 The phosphorescence lifetime diagram of the phosphorescent material prepared in Example 2 of the preparation method of the nano-confined enhanced biomass-based room temperature phosphorescent material of the present invention is shown. Figure 3 Examples 1-6 of the preparation method of the nano-confined enhanced biomass-based room temperature phosphorescent material of the present invention show the state of the phosphorescent material prepared under sunlight, under 365 nm ultraviolet light irradiation, and after the light is turned off. Figure 4 The phosphorescent material prepared in Example 2 of the preparation method of the nano-confined enhanced biomass-based room temperature phosphorescent material of the present invention is photographed in an advanced information encryption application. Detailed Implementation
[0019] The following detailed description is provided in conjunction with specific implementation methods.
[0020] The present invention discloses a method for preparing a nano-confined enhanced biomass-based room-temperature phosphorescent material, which uses collagen hydrolysate and two-dimensional layered nanosheets as raw materials and is prepared by a simple hydrothermal alkaline boiling method. The preparation process includes the following specific steps: Step 1: Add 4-6g of white skin powder to 200mL of deionized water, adjust the pH of the system to 10.0-13.0 with sodium hydroxide solution, stir magnetically at 45-60℃ for 4-6h, and after cooling to room temperature, centrifuge to obtain the supernatant solution, which is the collagen hydrolysate solution. Step 2: Under stirring conditions, add two-dimensional layered nanosheets to the transparent solution obtained in Step 1 (i.e., collagen hydrolysate solution) (maintaining the mass ratio of solid content in nanosheets to collagen hydrolysate at (1-5):400), stir for 20-60 min to obtain a transparent solution; the two-dimensional layered nanosheets are any one of lithium diatomite nanosheets, layered zirconium phosphate nanosheets, or layered bimetallic hydroxide nanosheets.
[0021] Step 3: Naturally dry the transparent solution obtained in Step 2 to obtain a light yellow solid, which can be ground to obtain a two-dimensional layered nano-confined induced enhanced biomass-based room temperature phosphorescent material.
[0022] Example 1 After soaking white skin powder in deionized water for 3 hours, the pH of the solution was adjusted to 10.0 with sodium hydroxide. The solution was then magnetically stirred at 55°C for 6 hours. After cooling to room temperature, the solution was centrifuged, and the supernatant was used to obtain a collagen hydrolysate solution. Next, a portion of the hydrolysate was taken, and lithium diatomaceous earth nanosheets were added to the solution, maintaining a solid content mass ratio of diatomaceous earth nanosheets to collagen hydrolysate of 1:400. The solution was stirred at room temperature for 20 minutes, naturally dried, and then ground to obtain a nano-confined enhanced biomass-based room-temperature phosphorescent material and its preparation method. Example 2 After soaking white skin powder in deionized water for 3 hours, the pH of the solution was adjusted to 13.0 with sodium hydroxide. The solution was then magnetically stirred at 45°C for 6 hours. After cooling to room temperature, the solution was centrifuged, and the supernatant was used to obtain a collagen hydrolysate solution. Next, a portion of the hydrolysate was taken, and zirconium phosphate nanosheets were added to the solution, maintaining a solid content mass ratio of 3:400 between the two-dimensional layered nanosheets and the collagen hydrolysate. The mixture was stirred at room temperature for 40 minutes, naturally dried, and ground to obtain a nano-confined enhanced biomass-based room-temperature phosphorescent material and its preparation method. Example 3 After soaking white skin powder in deionized water for 3 hours, the pH of the solution was adjusted to 13.0 with sodium hydroxide. The solution was then magnetically stirred at 60°C for 6 hours. After cooling to room temperature, the solution was centrifuged, and the supernatant was used to obtain a collagen hydrolysate solution. Next, a portion of the hydrolysate was taken, and zirconium phosphate nanosheets were added to the solution, maintaining a solid content mass ratio of 1:80 between the two-dimensional layered nanosheets and the collagen hydrolysate. The mixture was stirred at room temperature for 50 minutes, naturally dried, and ground to obtain a nano-confined enhanced biomass-based room-temperature phosphorescent material and its preparation method. Example 4 After soaking white skin powder in deionized water for 3 hours, the pH of the solution was adjusted to 11.0 with sodium hydroxide. The solution was then magnetically stirred at 55°C for 6 hours. After cooling to room temperature, the solution was centrifuged, and the supernatant was used to obtain a collagen hydrolysate solution. Next, a portion of the hydrolysate was taken, and layered bimetallic hydroxide nanosheets were added to the solution, maintaining a solid content mass ratio of 3:400 between the layered bimetallic hydroxide nanosheets and the collagen hydrolysate. The mixture was stirred at room temperature for 30 minutes, naturally dried, and ground to obtain a nano-confined enhanced biomass-based room-temperature phosphorescent material and its preparation method. Example 5 After soaking white skin powder in deionized water for 3 hours, the pH of the solution was adjusted to 12.0 with sodium hydroxide. The solution was then magnetically stirred at 60°C for 6 hours. After cooling to room temperature, the solution was centrifuged, and the supernatant was used to obtain a collagen hydrolysate solution. Next, a portion of the hydrolysate was taken, and zirconium phosphate nanosheets were added to the solution, maintaining a solid content ratio of 1:80 between the zirconium phosphate nanosheets and the collagen hydrolysate. The solution was stirred at room temperature for 60 minutes, naturally dried, and then ground to obtain a nano-confined enhanced biomass-based room-temperature phosphorescent material and its preparation method. Example 6 After soaking the white powder in deionized water for 3 hours, the pH of the solution was adjusted to 12.0 with sodium hydroxide. Then, the solution was magnetically stirred at 60°C for 6 hours. After cooling to room temperature, the solution was centrifuged, and the supernatant was obtained as a collagen hydrolysate solution. Next, a portion of the hydrolysate was taken, and lithium diatomaceous earth nanosheets were added to the solution. The mass ratio of the solid content in the lithium diatomaceous earth nanosheets to the collagen hydrolysate was kept at 1:80. The solution was stirred at room temperature for 30 minutes, naturally dried, and ground to obtain a nano-confined enhanced biomass-based room temperature phosphorescent material.
[0023] Figure 1 This is a TEM image of the phosphorescent material prepared in Example 2 of the preparation method of the nano-confined enhanced biomass-based room temperature phosphorescent material of the present invention. The image mainly shows the structure of the material prepared in Example 2, which is an organic-inorganic composite system, and the room temperature phosphorescence performance is enhanced by the confinement of nanosheets.
[0024] Figure 2 The phosphorescence lifetime diagram of the phosphorescent material prepared in Example 2 of the preparation method of the nano-confined enhanced biomass-based room temperature phosphorescent material of the present invention is shown in the figure. It can be seen from the figure that the prepared room temperature phosphorescent material has the significant characteristic of long lifetime.
[0025] Figure 3 Examples 1-6 of the preparation method of the nano-confined enhanced biomass-based room-temperature phosphorescent material of the present invention show the state of the phosphorescent materials prepared under sunlight, irradiation with a 365 nm ultraviolet lamp, and after the lamp is turned off. Figure 3 It can be seen that Example 2 exhibits the longest visible phosphorescence duration of 5.5s; the other Examples 1 and Examples 3-6 show that the visible phosphorescence duration of the prepared nano-confined enhanced biomass-based room temperature phosphorescent material and its preparation method is relatively short.
[0026] Figure 4This image shows a photograph of the phosphorescent material prepared in Example 2 of the preparation method for the nano-confined enhanced biomass-based room-temperature phosphorescent material of the present invention, applied to advanced information encryption applications. The present invention employs a component coating method to develop potential fingerprints, utilizing the effective mechanical adhesion of the biomass-based room-temperature phosphorescent material to the oily components of fingerprint residues, which are not easily visible during the day. When ultraviolet light is turned off, the green phosphorescent image of the fingerprint is clearly visible, with obvious bifurcation and rings. Figure 4 ).
[0027] Example 7 After soaking the white skin powder in deionized water for 3 hours, the pH of the solution was adjusted to 10.0 with sodium hydroxide. Then, the solution was magnetically stirred at 60°C for 6 hours. After cooling to room temperature, the solution was centrifuged, and the supernatant was obtained as a collagen hydrolysate solution. Next, a portion of the hydrolysate was taken, and lithium diatomaceous earth nanosheets were added to the above solution, maintaining a solid content mass ratio of lithium diatomaceous earth nanosheets to collagen hydrolysate of 1:80. The solution was stirred at room temperature for 30 minutes, naturally dried, and ground to obtain a nano-confined enhanced biomass-based room temperature phosphorescent material.
[0028] Example 8 After soaking the white skin powder in deionized water for 3 hours, the pH of the solution was adjusted to 10.0 with sodium hydroxide. Then, the solution was magnetically stirred at 50°C for 6 hours. After cooling to room temperature, the solution was centrifuged, and the supernatant was obtained as a collagen hydrolysate solution. Next, a portion of the hydrolysate was taken, and lithium diatomaceous earth nanosheets were added to the above solution, maintaining a solid content mass ratio of lithium diatomaceous earth nanosheets to collagen hydrolysate of 1:80. The solution was stirred at room temperature for 30 minutes, naturally dried, and ground to obtain a nano-confined enhanced biomass-based room temperature phosphorescent material.
[0029] Example 9 After soaking the white skin powder in deionized water for 3 hours, the pH of the solution was adjusted to 10.0 with sodium hydroxide. Then, the solution was magnetically stirred at 50°C for 5 hours. After cooling to room temperature, the solution was centrifuged, and the supernatant was obtained as a collagen hydrolysate solution. Next, a portion of the hydrolysate was taken, and lithium diatomaceous earth nanosheets were added to the above solution, maintaining a solid content mass ratio of lithium diatomaceous earth nanosheets to collagen hydrolysate of 1:80. The solution was stirred at room temperature for 30 minutes, naturally dried, and ground to obtain a nano-confined enhanced biomass-based room temperature phosphorescent material.
[0030] Example 10 After soaking the white skin powder in deionized water for 3 hours, the pH of the solution was adjusted to 10.0 with sodium hydroxide. Then, the solution was magnetically stirred at 55°C for 5 hours. After cooling to room temperature, the solution was centrifuged, and the supernatant was obtained as a collagen hydrolysate solution. Next, a portion of the hydrolysate was taken, and lithium diatomaceous earth nanosheets were added to the above solution, maintaining a solid content mass ratio of lithium diatomaceous earth nanosheets to collagen hydrolysate of 1:80. The solution was stirred at room temperature for 30 minutes, naturally dried, and ground to obtain a nano-confined enhanced biomass-based room temperature phosphorescent material.
[0031] Example 11 After soaking the white skin powder in deionized water for 3 hours, the pH of the solution was adjusted to 10.0 with sodium hydroxide. Then, the solution was magnetically stirred at 55°C for 5 hours. After cooling to room temperature, the solution was centrifuged, and the supernatant was obtained as a collagen hydrolysate solution. Next, a portion of the hydrolysate was taken, and lithium diatomaceous earth nanosheets were added to the above solution, maintaining a solid content mass ratio of lithium diatomaceous earth nanosheets to collagen hydrolysate of 1:300. The solution was stirred at room temperature for 30 minutes, naturally dried, and ground to obtain a nano-confined enhanced biomass-based room temperature phosphorescent material.
[0032] Example 12 After soaking the white skin powder in deionized water for 3 hours, the pH of the solution was adjusted to 10.0 with sodium hydroxide. Then, the solution was magnetically stirred at 55°C for 5 hours. After cooling to room temperature, the solution was centrifuged, and the supernatant was obtained as a collagen hydrolysate solution. Next, a portion of the hydrolysate was taken, and lithium diatomaceous earth nanosheets were added to the above solution, maintaining a solid content mass ratio of lithium diatomaceous earth nanosheets to collagen hydrolysate of 1:350. The solution was stirred at room temperature for 30 minutes, naturally dried, and ground to obtain a nano-confined enhanced biomass-based room temperature phosphorescent material.
[0033] Example 13 After soaking the white skin powder in deionized water for 3 hours, the pH of the solution was adjusted to 10.0 with sodium hydroxide. Then, the solution was magnetically stirred at 55°C for 5 hours. After cooling to room temperature, the solution was centrifuged, and the supernatant was used to obtain a collagen hydrolysate solution. Next, a portion of the hydrolysate was taken, and lithium diatomaceous earth nanosheets were added to the above solution, maintaining a solid content mass ratio of lithium diatomaceous earth nanosheets to collagen hydrolysate of 1:350. The solution was stirred at room temperature for 40 minutes, naturally dried, and ground to obtain a nano-confined enhanced biomass-based room temperature phosphorescent material.
[0034] Example 14 After soaking the white skin powder in deionized water for 3 hours, the pH of the solution was adjusted to 10.0 with sodium hydroxide. Then, the solution was magnetically stirred at 55°C for 5 hours. After cooling to room temperature, the solution was centrifuged, and the supernatant was obtained as a collagen hydrolysate solution. Next, a portion of the hydrolysate was taken, and lithium diatomaceous earth nanosheets were added to the above solution, maintaining a solid content mass ratio of lithium diatomaceous earth nanosheets to collagen hydrolysate of 1:350. The solution was stirred at room temperature for 30 minutes, naturally dried, and ground to obtain a nano-confined enhanced biomass-based room temperature phosphorescent material.
[0035] Example 15 After soaking the white skin powder in deionized water for 3 hours, the pH of the solution was adjusted to 10.0 with sodium hydroxide. Then, the solution was magnetically stirred at 60°C for 5 hours. After cooling to room temperature, the solution was centrifuged, and the supernatant was obtained as a collagen hydrolysate solution. Next, a portion of the hydrolysate was taken, and lithium diatomaceous earth nanosheets were added to the above solution, maintaining a solid content mass ratio of lithium diatomaceous earth nanosheets to collagen hydrolysate of 1:350. The solution was stirred at room temperature for 30 minutes, naturally dried, and ground to obtain a nano-confined enhanced biomass-based room temperature phosphorescent material.
[0036] Example 16 After soaking the white skin powder in deionized water for 3 hours, the pH of the solution was adjusted to 10.0 with sodium hydroxide. Then, the solution was magnetically stirred at 60°C for 5 hours. After cooling to room temperature, the solution was centrifuged, and the supernatant was obtained as a collagen hydrolysate solution. Next, a portion of the hydrolysate was taken, and lithium diatomaceous earth nanosheets were added to the above solution, maintaining a solid content mass ratio of lithium diatomaceous earth nanosheets to collagen hydrolysate of 1:350. The solution was stirred at room temperature for 40 minutes, naturally dried, and ground to obtain a nano-confined enhanced biomass-based room temperature phosphorescent material.
[0037] Example 17 After soaking the white skin powder in deionized water for 3 hours, the pH of the solution was adjusted to 10.0 with sodium hydroxide. Then, the solution was magnetically stirred at 60°C for 5 hours. After cooling to room temperature, the solution was centrifuged, and the supernatant was obtained as a collagen hydrolysate solution. Next, a portion of the hydrolysate was taken, and lithium diatomaceous earth nanosheets were added to the above solution, maintaining a solid content mass ratio of lithium diatomaceous earth nanosheets to collagen hydrolysate of 1:350. The solution was stirred at room temperature for 50 minutes, naturally dried, and ground to obtain a nano-confined enhanced biomass-based room temperature phosphorescent material.
[0038] This invention utilizes a simple hydrothermal alkaline boiling method to obtain organic phosphorescent materials with afterglow effects at near room temperature, reducing the need for high temperature, high pressure, or chemical reagents, while avoiding the high energy consumption and high pollution problems of conventional methods for obtaining organic phosphorescent materials.
Claims
1. A method for preparing nano-confined enhanced biomass-based room-temperature phosphorescent materials, characterized in that, Specifically, the steps include the following: Step 1: Add white skin powder to deionized water, adjust the pH of the system with sodium hydroxide solution, stir magnetically under heating conditions, and after cooling to room temperature, centrifuge to obtain the supernatant, which is the collagen hydrolysate solution. Step 2: Under stirring conditions, add two-dimensional layered nanosheets to the collagen hydrolysate solution obtained in Step 1 and stir to obtain a transparent solution; Step 3: Naturally dry the transparent solution obtained in Step 2 to obtain a light yellow solid, which can be ground to obtain a two-dimensional layered nano-confined induced enhanced biomass-based room temperature phosphorescent material.
2. The method for preparing the nano-confined enhanced biomass-based room temperature phosphorescent material according to claim 1, characterized in that, In step 1, the pH of the system is adjusted to 10.0-13.0 using sodium hydroxide solution.
3. The method for preparing the nano-confined enhanced biomass-based room temperature phosphorescent material according to claim 1, characterized in that, In step 1, the heating temperature is 45-60℃.
4. The method for preparing the nano-confined enhanced biomass-based room-temperature phosphorescent material according to claim 1, characterized in that, In step 1, the stirring time is 4-6 hours.
5. The method for preparing the nano-confined enhanced biomass-based room-temperature phosphorescent material according to claim 1, characterized in that, In step 2, the two-dimensional layered nanosheets are any one of lithium diatomite nanosheets, layered zirconium phosphate nanosheets, or layered bimetallic hydroxide nanosheets.
6. The method for preparing the nano-confined enhanced biomass-based room-temperature phosphorescent material according to claim 1, characterized in that, In step 2, the mass ratio of solid content in the two-dimensional layered nanosheets and collagen hydrolysate is 1-5:
400.
7. The method for preparing the nano-confined enhanced biomass-based room-temperature phosphorescent material according to claim 1, characterized in that, In step 2, the stirring time is 20-60 minutes.
8. A nano-confined enhanced biomass-based room temperature phosphorescent material, prepared by the preparation method of the nano-confined enhanced biomass-based room temperature phosphorescent material as described in any one of claims 1 to 7.
9. Application of nano-confined enhanced biomass-based room temperature phosphorescent materials in anti-counterfeiting and information encryption.