Preparation method of amorphous photonic crystal composite material with photoelectric double-response performance

Abstract

The invention discloses a preparation method of an amorphous photonic crystal composite material with photoelectric double response performance, which comprises the following steps: etching Ti3AlC2 to obtain multiple layers of MXene; a single-layer Ti < 3 > C < 2 > T < x > MXene nanosheet is obtained through an ion intercalation method and a stripping process; the preparation method comprises the following steps: mixing a ground single-layer Ti < 3 > C < 2 > T < x > MXene nanosheet, poly (styrene-butyl acrylate-acrylic acid) microspheres, N-hydroxyethyl acrylamide, phenyl-2, 4, 6-trimethylbenzoyl lithium phosphinate, glycerol and deionized water, so as to obtain an amorphous photonic crystal composite material; poly (styrene-butyl acrylate-acrylic acid) microspheres are adopted to construct an amorphous photonic crystal structure, a single-layer Ti3C2Tx MXene nanosheet is doped to serve as a conductive functional component, optical stimulation and mechanical deformation can be responded at the same time, and good photoelectric double-response performance, high response speed and structural design flexibility are achieved.

Description

Technical Field

[0001] This invention belongs to the field of composite material technology, specifically relating to a method for preparing an amorphous photonic crystal composite material with photoelectric dual response properties. Background Technology

[0002] With the rapid development of smart wearable devices, medical monitoring instruments, and environmental sensing systems, the demand for integrated, multifunctional, and highly sensitive sensors is increasing. Especially in complex environments, achieving synchronous detection and response to optical and electrical signals is of great significance for improving the intelligence level of equipment and the efficiency of information acquisition.

[0003] However, existing multi-signal sensing systems typically require separate designs using different materials and structural units. For example, optical signal detection often relies on photosensitive semiconductors and organic photoconductive materials, while electrical signal detection often uses conductive polymers or metal oxides as conductive media. This "separate construction" approach not only leads to complex material systems and increased manufacturing costs but also increases the difficulty of structural integration and processing requirements. Furthermore, the collaborative use of multiple materials often faces problems such as poor interface stability and insufficient flexibility, making it difficult to meet the application needs of current diverse scenarios.

[0004] MXene, a conductive two-dimensional material, has gained widespread attention in the fields of flexible electronics and sensors due to its metallic conductivity, high specific surface area, and mechanical flexibility. Meanwhile, amorphous photonic crystal materials with tunable structural color and angle-independent optical properties offer new avenues for realizing visual feedback sensors.

[0005] With the increasing maturity of 3D printing manufacturing technology, how to integrate functional components with electrical and optical structural response capabilities into a composite structure that can be precisely molded and mass-produced has become an important research direction in the field of flexible multifunctional sensors.

[0006] Therefore, there is an urgent need to develop a flexible sensing platform with uniform material structure, simplified manufacturing process, and good photoelectric synergistic response capability to meet the needs of multidimensional signal acquisition and real-time monitoring in complex environments. Summary of the Invention

[0007] The purpose of this invention is to provide a method for preparing an amorphous photonic crystal composite material with photoelectric dual response properties, so as to solve the problems mentioned in the background art.

[0008] To achieve the above objectives, the present invention provides the following technical solution: a method for preparing an amorphous photonic crystal composite material with photoelectric dual-response properties, comprising the following steps: Step 1: Etch Ti3AlC2 with an etching solution to obtain multilayer MXene; Step 2: Obtain monolayer Ti3C2T through ion intercalation and exfoliation processes. x MXene nanosheets; Step 3: Add potassium persulfate aqueous solution to a mixed emulsion of styrene monomer, butyl acrylate, acrylic acid, sodium dodecyl sulfate and deionized water to obtain poly(styrene-butyl acrylate-acrylic acid) microspheres; Step 4: Grind the single-layer Ti3C2T x An amorphous photonic crystal composite material was obtained by mixing MXene nanosheets, poly(styrene-butyl acrylate-acrylic acid) microspheres, N-hydroxyethyl acrylamide, lithium phenyl-2,4,6-trimethylbenzoylphosphinate, glycerol, and deionized water.

[0009] Preferably, step 1 specifically includes the following steps: Step 1.1: Add hydrochloric acid and lithium fluoride to a polytetrafluoroethylene container and stir and mix under oil bath conditions to form an etching solution; Step 1.2: Add Ti3AlC2 precursor powder to the etching solution and stir the mixture under constant temperature to remove the Al layer. Step 1.3: Centrifuge the reaction mixture from Step 1.2 and wash it with deionized water until neutral to obtain multilayer MXene.

[0010] Preferably, the amount of hydrochloric acid added is 20 mL, the amount of lithium fluoride added is 1-1.4 g, and the amount of Ti3AlC2 precursor powder added is 1-1.4 g.

[0011] Preferably, step 2 specifically includes the following steps: Step 2.1: Lithium chloride and deionized water are mixed with multilayer MXene using an ion intercalation method; Step 2.2: After standing, shake to peel off the multilayer MXene; Step 2.3: Centrifugation removes impurities, followed by freeze-drying to obtain a monolayer of Ti3C2T. x MXene nanosheets.

[0012] Preferably, the amount of lithium chloride added is 1.2-1.6g, and the amount of deionized water added is 20mL.

[0013] Preferably, step 3 specifically includes the following steps: Step 3.1: Add deionized water, sodium dodecyl sulfate, and sodium bicarbonate to a three-necked flask, and stir to dissolve and form a reaction system; Step 3.2: Under heating and stirring conditions, slowly add the fully emulsified emulsion A dropwise into a three-necked flask, while simultaneously adding potassium persulfate aqueous solution dropwise using a dual-channel syringe to initiate the polymerization reaction; Step 3.3: Under heating and stirring conditions, slowly add the fully emulsified emulsion B dropwise into a three-necked flask, while simultaneously adding potassium persulfate aqueous solution dropwise using a dual-channel syringe to initiate the polymerization reaction; Step 3.4: Remove impurities from the reaction emulsion to obtain poly(styrene-butyl acrylate-acrylic acid) microspheres.

[0014] Preferably, emulsion A comprises: styrene monomer, butyl acrylate, acrylic acid, sodium lauryl sulfate, and deionized water, wherein the amount of styrene monomer added is 30-40g, the amount of butyl acrylate added is 9-12g, the amount of acrylic acid added is 4.5g, the amount of sodium lauryl sulfate added is 0.09-0.12g, and the content of deionized water is 7.5-10g. Preferably, the emulsion B comprises: styrene monomer, butyl acrylate, acrylic acid, sodium dodecyl sulfate, and deionized water, wherein the amount of styrene monomer added is 90-110g, the amount of butyl acrylate added is 18-21g, the amount of acrylic acid added is 4.5g, the amount of sodium dodecyl sulfate added is 0.3-0.4g, and the content of deionized water is 15-17g.

[0015] Preferably, the concentration of the potassium persulfate solution is 3.5 wt%, and the amount of potassium persulfate solution added is 5-7 ml.

[0016] Preferably, the amorphous photonic crystal composite material contains a single layer of Ti3C2T. x The concentration of MXene nanosheets is 1.5-1.7 mg / ml, the concentration of poly(styrene-butyl acrylate-acrylic acid) microspheres is 20-25 wt%, the content of N-hydroxyethylacrylamide is 15 wt%, the content of phenyl-2,4,6-trimethylbenzoyl lithium phosphinate is 0.15 wt%, and the content of glycerol is 15 wt%.

[0017] The technical effects and advantages of this invention are as follows: 1. An amorphous photonic crystal structure was constructed using poly(styrene-butyl acrylate-acrylic acid) microspheres and doped with a monolayer of Ti3C2T. x As a conductive functional component, MXene nanosheets can respond to both optical stimuli and mechanical deformation, exhibiting excellent photoelectric dual-response performance, fast response speed, and structural design flexibility. 2. By adopting an amorphous photonic crystal structure, it exhibits angle-independent structural color performance, effectively eliminating signal deviation caused by changes in observation angle, thereby achieving higher accuracy in light response visualization feedback. It performs excellently in terms of structural uniformity, manufacturing process simplicity, and functional integration, and is suitable for various application scenarios such as flexible electronics, wearable devices, and environmental monitoring, significantly reducing system complexity and manufacturing costs. Attached Figure Description

[0018] Figure 1 This is a SEM image of the monolayer MXene nanosheets of the present invention; Figure 2 The images show the SEM image and the Fast Fourier Transform analysis diagram of the flexible sensor of this invention. Figure 3 This is a photograph of the complex hollow structure printed from multiple materials according to the present invention; Figure 4 Image a shows a photograph of the flexible sensor in an environment with humidity levels ranging from 20% to 100%, along with the corresponding reflectance spectrum. Figure 4 b is the electrical signal response diagram of the flexible sensor to different bending angles of the finger joint. Detailed Implementation

[0019] The following will refer to the appendices in the embodiments of the present invention. Figure 1-4 The technical solutions in the embodiments of the present invention are clearly and completely described herein. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0020] This invention provides, for example Figures 1-4 The method for preparing an amorphous photonic crystal composite material with photoelectric dual response properties, as shown, includes the following steps: Step 1: Etch Ti3AlC2 with an etching solution to obtain multilayer MXene; Step 2: Obtain monolayer Ti3C2T through ion intercalation and exfoliation processes. x MXene nanosheets; Step 3: Add potassium persulfate aqueous solution to a mixed emulsion of styrene monomer, butyl acrylate, acrylic acid, sodium dodecyl sulfate and deionized water to obtain poly(styrene-butyl acrylate-acrylic acid) microspheres; Step 4: Grind the single-layer Ti3C2T x An amorphous photonic crystal composite material was obtained by mixing MXene nanosheets, poly(styrene-butyl acrylate-acrylic acid) microspheres, N-hydroxyethyl acrylamide, lithium phenyl-2,4,6-trimethylbenzoylphosphinate, glycerol, and deionized water.

[0021] Specifically, step 1 includes the following steps: Step 1.1: Add hydrochloric acid and lithium fluoride to a polytetrafluoroethylene container and stir and mix under oil bath conditions to form an etching solution; Step 1.2: Add Ti3AlC2 precursor powder to the etching solution and stir the mixture under constant temperature to remove the Al layer. Step 1.3: Centrifuge the reaction mixture from step 1.2, wash with deionized water until neutral (pH=7), and obtain multilayer MXene.

[0022] Specifically, the amount of hydrochloric acid added is 20 mL, the amount of lithium fluoride added is 1-1.4 g, and the amount of Ti3AlC2 precursor powder added is 1-1.4 g.

[0023] Specifically, step 2 includes the following steps: Step 2.1: Lithium chloride and deionized water are mixed with multilayer MXene using an ion intercalation method; Step 2.2: After standing, shake to peel off the multilayer MXene; Step 2.3: Centrifugation removes impurities, followed by freeze-drying to obtain a monolayer of Ti3C2T. x MXene nanosheets.

[0024] Specifically, the amount of lithium chloride added is 1.2-1.6g, and the amount of deionized water added is 20mL.

[0025] Specifically, step 3 includes the following steps: Step 3.1: Add deionized water, sodium dodecyl sulfate, and sodium bicarbonate to a three-necked flask, and stir to dissolve and form a reaction system; Step 3.2: Under heating and stirring conditions, slowly add the fully emulsified emulsion A dropwise into a three-necked flask, while simultaneously adding potassium persulfate aqueous solution dropwise using a dual-channel syringe to initiate the polymerization reaction; Step 3.3: Under heating and stirring conditions, slowly add the fully emulsified emulsion B dropwise into a three-necked flask, while simultaneously adding potassium persulfate aqueous solution dropwise using a dual-channel syringe to initiate the polymerization reaction; Step 3.4: Remove impurities from the reaction emulsion to obtain poly(styrene-butyl acrylate-acrylic acid) microspheres.

[0026] Specifically, emulsion A comprises: styrene monomer, butyl acrylate, acrylic acid, sodium lauryl sulfate, and deionized water, wherein the amount of styrene monomer added is 30-40g, the amount of butyl acrylate added is 9-12g, the amount of acrylic acid added is 4.5g, the amount of sodium lauryl sulfate added is 0.09-0.12g, and the content of deionized water is 7.5-10g. Specifically, the emulsion B comprises: styrene monomer, butyl acrylate, acrylic acid, sodium dodecyl sulfate, and deionized water, wherein the amount of styrene monomer added is 90-110g, the amount of butyl acrylate added is 18-21g, the amount of acrylic acid added is 4.5g, the amount of sodium dodecyl sulfate added is 0.3-0.4g, and the content of deionized water is 15-17g.

[0027] Specifically, the concentration of the potassium persulfate solution is 3.5 wt%, and the amount of potassium persulfate solution added is 5-7 ml.

[0028] Specifically, the monolayer Ti3C2T in the amorphous photonic crystal composite material x The concentration of MXene nanosheets is 1.5-1.7 mg / ml, the concentration of poly(styrene-butyl acrylate-acrylic acid) microspheres is 20-25 wt%, the content of N-hydroxyethylacrylamide is 15 wt%, the content of phenyl-2,4,6-trimethylbenzoyl lithium phosphinate is 0.15 wt%, and the content of glycerol is 15 wt%.

[0029] In this invention, the obtained amorphous photonic crystal composite material can be photocured to form a photocurable composite hydrogel ink. The composite hydrogel ink can be 3D printed using a digital light processing (DLP) photocuring 3D printing method through a layer-by-layer curing process. The light source of the photocuring printer is 405 nm ultraviolet light, with a light intensity set to 5 mW / cm². 2 Each layer is set to a height of 100 μm and a curing time of 12 s. After printing, the layers are rinsed with deionized water to obtain a flexible fabrication with amorphous photonic structure and photoelectric dual response properties.

[0030] This invention utilizes poly(styrene-butyl acrylate-acrylic acid) microspheres to construct an amorphous photonic crystal structure and dops it with a monolayer of Ti3C2T. x MXene nanosheets, as conductive functional components, enable the fabrication of devices that can simultaneously detect and respond to optical and electrical signals. They can generate structural color responses to changes in environmental humidity and output electrical signals in response to changes in external stress, exhibiting excellent dual-response characteristics. This makes them suitable for wearable devices, environmental sensing, and flexible electronics. In this invention, by selecting poly(styrene-butyl acrylate-acrylic acid) microspheres of different sizes to form an amorphous photonic crystal array with different structural colors, it is possible to print and prepare parts of different colors.

[0031] Example 1: 20 mL of hydrochloric acid and 1.1 g of lithium fluoride were added to a polytetrafluoroethylene container, and the mixture was magnetically stirred for 10 min in an oil bath at 42°C to form an etching solution. Then, 1.1 g of Ti3AlC2 powder was added, and the mixture was magnetically stirred at 500 rpm for 24 h at 42°C to remove the Al layer. After the reaction was complete, the mixture was centrifuged at 3000 rpm for 5 min, the precipitate was collected, and the precipitate was repeatedly washed with deionized water until the pH of the washing solution reached 7, yielding multilayer MXene.

[0032] The obtained multilayer MXene was mixed with 1.2 g of lithium chloride and 20 mL of deionized water, and after standing for 5 min, it was shaken. Single-layer MXene nanosheets were prepared by ion intercalation exfoliation. The exfoliated mixture was first centrifuged at 6000 rpm to remove impurities, then centrifuged at 9000 rpm for 10 min. Finally, the precipitate was placed in a freeze dryer for drying to obtain single-layer Ti3C2T. x MXene nanosheets.

[0033] Add 130 mL of deionized water, 0.08 g of sodium dodecyl sulfate and 0.65 g of sodium bicarbonate to a 1000 mL three-necked flask. Stir magnetically at 250 rpm for 30 min in an oil bath at 25°C to fully dissolve the components and form a polymerization reaction medium.

[0034] Preparation of Emulsion A: 40 g styrene, 12 g butyl acrylate, 4.5 g acrylic acid, 0.12 g sodium dodecyl sulfate, and 10 g deionized water were added to a beaker and emulsified using a magnetic stirrer at 250 rpm for 6 min to obtain a homogeneous emulsion A. Emulsion A was then slowly added dropwise to a three-necked flask while maintaining a constant stirring speed, and the reaction was carried out at 85°C. A 3.5 wt% potassium persulfate aqueous solution was added dropwise at a rate of 30 mL / h using a dual-channel syringe, with a total added volume of 7 mL, to initiate the monomer polymerization reaction in emulsion A.

[0035] After emulsion A was added dropwise and reacted for 60 min, emulsion B was prepared: 110 g styrene, 21 g butyl acrylate, 4.5 g acrylic acid, 0.4 g sodium dodecyl sulfate, and 17 g deionized water were mixed and emulsified at 250 rpm for 7 min to obtain a homogeneous emulsion B. Emulsion B was added dropwise to a three-necked flask, and a 3.5 wt% potassium persulfate aqueous solution was added dropwise at the same rate, with a total volume of 10 mL. The reaction was continued at 96°C for 4 h to complete the polymerization. After the reaction was completed, the reaction solution was filtered through a 1000-mesh filter, and the filtrate was centrifuged at 12000 rpm for 2 h to remove impurities, resulting in an aqueous dispersion of poly(styrene-butyl acrylate-acrylic acid) microspheres with a diameter of approximately 258 nm, i.e., an aqueous dispersion of P(St-BA-AA) microspheres.

[0036] After grinding monolayer MXene nanosheets, they were added to the system at a concentration of 1.7 mg / mL. The system consisted of 15 wt% N-hydroxyethylacrylamide monomer, 20 wt% P(St-BA-AA) microspheres with a diameter of approximately 258 nm, 0.15 wt% photoinitiator LAP, 15 wt% glycerol, and the balance deionized water. The mixed solution was ultrasonicated for 1 h and magnetically stirred for 1 h to ensure thorough and uniform dispersion, thus preparing an amorphous photonic crystal composite material.

[0037] This amorphous photonic crystal composite material is suitable for use as a composite ink in digital light processing (DLP) 3D printing. The ink was loaded into a 405 nm wavelength photopolymerization printer and printed layer by layer under conditions of 5 mW / cm² light intensity, 100 μm layer height, and 12 s single-layer exposure time. After printing, the sample surface was rinsed with deionized water, yielding a flexible sensor with photoelectric dual-response properties exhibiting a red structural color.

[0038] Example 2: 20 mL of hydrochloric acid and 1.4 g of lithium fluoride were added to a polytetrafluoroethylene container and magnetically stirred for 10 min in an oil bath at 42°C to form an etching solution. Then, 1.4 g of Ti3AlC2 powder was added, and the mixture was magnetically stirred at 500 rpm for 24 h at 42°C to remove the Al layer. After the reaction was complete, the mixture was centrifuged at 3000 rpm for 5 min, the precipitate was collected, and the solution was repeatedly washed with deionized water until the pH of the washing solution reached 7, yielding multilayer MXene.

[0039] The obtained multilayer MXene was mixed with 1.2 g lithium chloride and 20 mL deionized water, and after standing for 5 min, it was shaken. Single-layer MXene nanosheets were prepared by ion intercalation exfoliation. The exfoliated mixture was first centrifuged at 6000 rpm to remove impurities, and then centrifuged at 9000 rpm for 10 min. Finally, the precipitate was placed in a freeze dryer for drying to obtain single-layer Ti3C2Tx MXene nanosheets.

[0040] Add 130 mL of deionized water, 0.08 g of sodium dodecyl sulfate and 0.65 g of sodium bicarbonate to a 1000 mL three-necked flask. Stir magnetically at 250 rpm for 30 min in an oil bath at 25°C to fully dissolve the components and form a polymerization reaction medium.

[0041] Preparation of Emulsion A: 35 g styrene, 10 g butyl acrylate, 4.5 g acrylic acid, 0.1 g sodium dodecyl sulfate, and 9 g deionized water were added to a beaker and emulsified using a magnetic stirrer at 250 rpm for 6 min to obtain a homogeneous emulsion A. Emulsion A was then slowly added dropwise to a three-necked flask while maintaining a constant stirring speed, and the reaction was carried out at 85°C. A 3.5 wt% potassium persulfate aqueous solution was added dropwise at a rate of 30 mL / h using a dual-channel syringe, with a total added volume of 6 mL, to initiate the monomer polymerization reaction in emulsion A.

[0042] After emulsion A was added dropwise and reacted for 50 min, emulsion B was prepared: 100 g styrene, 20 g butyl acrylate, 4.5 g acrylic acid, 0.35 g sodium dodecyl sulfate, and 16 g deionized water were mixed and emulsified at 250 rpm for 7 min to obtain a homogeneous emulsion B. Emulsion B was added dropwise to a three-necked flask, and a 3.5 wt% potassium persulfate aqueous solution was added dropwise at the same rate, with a total volume of 10 mL. The reaction was continued at 96°C for 4 h to complete the polymerization. After the reaction was completed, the reaction solution was filtered through a 1000-mesh filter, and the filtrate was centrifuged at 12000 rpm for 2 h to remove impurities, resulting in an aqueous dispersion of poly(styrene-butyl acrylate-acrylic acid) microspheres with a diameter of approximately 236 nm, i.e., an aqueous dispersion of P(St-BA-AA) microspheres.

[0043] After grinding monolayer MXene nanosheets, they were added to the system at a concentration of 1.6 mg / mL. The system consisted of 15 wt% N-hydroxyethylacrylamide monomer, 25 wt% P(St-BA-AA) microspheres with a diameter of approximately 236 nm, 0.15 wt% photoinitiator LAP, 15 wt% glycerol, and the balance deionized water. The mixed solution was ultrasonicated for 1 h and magnetically stirred for 1 h to ensure thorough and uniform dispersion, thus preparing an amorphous photonic crystal composite material.

[0044] This amorphous photonic crystal composite material is suitable for use as a composite ink in digital light processing (DLP) 3D printing. The ink was loaded into a 405 nm wavelength photopolymerization printer and printed layer by layer under conditions of 5 mW / cm² light intensity, 100 μm layer height, and 12 s single-layer exposure time. After printing, the sample surface was rinsed with deionized water, yielding a flexible sensor with green structural color and photoelectric dual-response properties.

[0045] Example 3: 20 mL of hydrochloric acid and 1.0 g of lithium fluoride were added to a polytetrafluoroethylene container, and the mixture was magnetically stirred for 10 min in an oil bath at 42°C to form an etching solution. Then, 1.0 g of Ti3AlC2 powder was added, and the mixture was magnetically stirred at 500 rpm for 24 h at 42°C to remove the Al layer. After the reaction was complete, the mixture was centrifuged at 3000 rpm for 5 min, the precipitate was collected, and the precipitate was repeatedly washed with deionized water until the pH of the washing solution reached 7, yielding multilayer MXene.

[0046] The obtained multilayer MXene was mixed with 1.2 g lithium chloride and 20 mL deionized water, and after standing for 5 min, it was shaken. Single-layer MXene nanosheets were prepared by ion intercalation exfoliation. The exfoliated mixture was first centrifuged at 6000 rpm to remove impurities, and then centrifuged at 9000 rpm for 10 min. Finally, the precipitate was placed in a freeze dryer for drying to obtain single-layer Ti3C2Tx MXene nanosheets.

[0047] Add 130 mL of deionized water, 0.08 g of sodium dodecyl sulfate and 0.65 g of sodium bicarbonate to a 1000 mL three-necked flask. Stir magnetically at 250 rpm for 30 min in an oil bath at 25°C to fully dissolve the components and form a polymerization reaction medium.

[0048] Preparation of Emulsion A: 30 g styrene, 9 g butyl acrylate, 4.5 g acrylic acid, 0.09 g sodium dodecyl sulfate, and 7.5 g deionized water were added to a beaker and emulsified using a magnetic stirrer at 250 rpm for 5 min to obtain a homogeneous emulsion A. Emulsion A was then slowly added dropwise to a three-necked flask while maintaining a constant stirring speed, and the reaction was carried out at 85°C. A 3.5 wt% potassium persulfate aqueous solution was added dropwise at a rate of 30 mL / h using a dual-channel syringe, with a total added volume of 5 mL, to initiate the monomer polymerization reaction in emulsion A.

[0049] After emulsion A was added dropwise and reacted for 40 min, emulsion B was prepared: 90 g styrene, 18 g butyl acrylate, 4.5 g acrylic acid, 0.3 g sodium dodecyl sulfate, and 15 g deionized water were mixed and emulsified at 250 rpm for 7 min to obtain a homogeneous emulsion B. Emulsion B was added dropwise to a three-necked flask, and a 3.5 wt% potassium persulfate aqueous solution was added dropwise at the same rate, with a total volume of 10 mL. The reaction was continued at 96°C for 4 h to complete the polymerization. After the reaction was completed, the reaction solution was filtered through a 1000-mesh filter, and the filtrate was centrifuged at 12000 rpm for 2 h to remove impurities, resulting in an aqueous dispersion of poly(styrene-butyl acrylate-acrylic acid) microspheres with a diameter of approximately 215 nm, i.e., an aqueous dispersion of P(St-BA-AA) microspheres.

[0050] After grinding monolayer MXene nanosheets, they were added to the system at a concentration of 1.6 mg / mL. The system consisted of 15 wt% N-hydroxyethylacrylamide monomer, 20 wt% P(St-BA-AA) microspheres with a diameter of approximately 215 nm, 0.15 wt% photoinitiator LAP, 15 wt% glycerol, and the balance deionized water. The mixed solution was ultrasonicated for 1 h and magnetically stirred for 1 h to ensure thorough and uniform dispersion, thus preparing the photonic crystal composite material.

[0051] This amorphous photonic crystal composite material is suitable for use as a composite ink in digital light processing (DLP) 3D printing. The ink was loaded into a 405 nm wavelength photopolymerization printer and printed layer by layer under conditions of 5 mW / cm² light intensity, 100 μm layer height, and 12 s single-layer exposure time. After printing, the sample surface was rinsed with deionized water to obtain a flexible sensor with photoelectric dual-response properties exhibiting a blue structural color.

[0052] Finally, it should be noted that the above description 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 foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing an amorphous photonic crystal composite material with photoelectric dual-response properties, characterized in that, Includes the following steps: Step 1: Etch Ti3AlC2 with an etching solution to obtain multilayer MXene; Step 2: Obtain monolayer Ti3C2T through ion intercalation and exfoliation processes. x MXene nanosheets; Step 3: Add potassium persulfate aqueous solution to a mixed emulsion of styrene monomer, butyl acrylate, acrylic acid, sodium dodecyl sulfate and deionized water to obtain poly(styrene-butyl acrylate-acrylic acid) microspheres; Step 4: Grind the single-layer Ti3C2T x An amorphous photonic crystal composite material was obtained by mixing MXene nanosheets, poly(styrene-butyl acrylate-acrylic acid) microspheres, N-hydroxyethyl acrylamide, lithium phenyl-2,4,6-trimethylbenzoylphosphinate, glycerol, and deionized water.

2. The method for preparing an amorphous photonic crystal composite material with photoelectric dual-response properties according to claim 1, characterized in that, Step 1 specifically includes the following steps: Step 1.1: Add hydrochloric acid and lithium fluoride to a polytetrafluoroethylene container and stir and mix under oil bath conditions to form an etching solution; Step 1.2: Add Ti3AlC2 precursor powder to the etching solution and stir the mixture under constant temperature to remove the Al layer. Step 1.3: Centrifuge the reaction mixture from Step 1.2 and wash it with deionized water until neutral to obtain multilayer MXene.

3. The method for preparing an amorphous photonic crystal composite material with photoelectric dual-response properties according to claim 2, characterized in that, The amount of hydrochloric acid added is 20 mL, the amount of lithium fluoride added is 1-1.4 g, and the amount of Ti3AlC2 precursor powder added is 1-1.4 g.

4. The method for preparing an amorphous photonic crystal composite material with photoelectric dual-response properties according to claim 1, characterized in that, Step 2 specifically includes the following steps: Step 2.1: Lithium chloride and deionized water are mixed with multilayer MXene using an ion intercalation method; Step 2.2: After standing, shake to peel off the multilayer MXene; Step 2.3: Centrifugation removes impurities, followed by freeze-drying to obtain a monolayer of Ti3C2T. x MXene nanosheets.

5. The method for preparing an amorphous photonic crystal composite material with photoelectric dual-response properties according to claim 4, characterized in that, The amount of lithium chloride added is 1.2-1.6g, and the amount of deionized water added is 20mL.

6. The method for preparing an amorphous photonic crystal composite material with photoelectric dual-response properties according to claim 1, characterized in that, Step 3 specifically includes the following steps: Step 3.1: Add deionized water, sodium dodecyl sulfate, and sodium bicarbonate to a three-necked flask, and stir to dissolve and form a reaction system; Step 3.2: Under heating and stirring conditions, slowly add the fully emulsified emulsion A dropwise into a three-necked flask, while simultaneously adding potassium persulfate aqueous solution dropwise using a dual-channel syringe to initiate the polymerization reaction; Step 3.3: Under heating and stirring conditions, slowly add the fully emulsified emulsion B dropwise into a three-necked flask, while simultaneously adding potassium persulfate aqueous solution dropwise using a dual-channel syringe to initiate the polymerization reaction; Step 3.4: Remove impurities from the reaction emulsion to obtain poly(styrene-butyl acrylate-acrylic acid) microspheres.

7. The method for preparing an amorphous photonic crystal composite material with photoelectric dual-response properties according to claim 6, characterized in that, Emulsion A comprises: styrene monomer, butyl acrylate, acrylic acid, sodium dodecyl sulfate, and deionized water, wherein the amount of styrene monomer added is 30-40g, the amount of butyl acrylate added is 9-12g, the amount of acrylic acid added is 4.5g, the amount of sodium dodecyl sulfate added is 0.09-0.12g, and the content of deionized water is 7.5-10g.

8. The method for preparing an amorphous photonic crystal composite material with photoelectric dual-response properties according to claim 6, characterized in that, Emulsion B comprises: styrene monomer, butyl acrylate, acrylic acid, sodium dodecyl sulfate, and deionized water, wherein the amount of styrene monomer added is 90-110g, the amount of butyl acrylate added is 18-21g, the amount of acrylic acid added is 4.5g, the amount of sodium dodecyl sulfate added is 0.3-0.4g, and the content of deionized water is 15-17g.

9. The method for preparing an amorphous photonic crystal composite material with photoelectric dual-response properties according to claim 6, characterized in that, The concentration of the potassium persulfate solution is 3.5 wt%, and the amount of potassium persulfate solution added is 5-7 ml.

10. The method for preparing an amorphous photonic crystal composite material with photoelectric dual-response properties according to claim 1, characterized in that, The monolayer Ti3C2T in the amorphous photonic crystal composite material x The concentration of MXene nanosheets is 1.5-1.7 mg / ml, the concentration of poly(styrene-butyl acrylate-acrylic acid) microspheres is 20-25 wt%, the content of N-hydroxyethylacrylamide is 15 wt%, the content of phenyl-2,4,6-trimethylbenzoyl lithium phosphinate is 0.15 wt%, and the content of glycerol is 15 wt%.

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