Mesoporous silica-based core-shell heterojunction material, preparation method and application

Abstract

The application discloses a kind of core-shell heterojunction materials based on mesoporous silica, preparation method and application. With mesoporous silica as base template material, its surface is modified grafting by cationic surfactant, make mesoporous silica surface and hole cover a layer of gold source in gold seed solution, realize in-situ synthesis of gold nanoparticles in mesoporous silica hole under the action of reducing agent;Again, in the growth solution of molybdenum source and sulfur source, gold-loaded mesoporous silica surface is in-situ grown with hydrothermal method MoS2 coating, and MoS2 / gold-mesoporous silica core-shell heterojunction material is obtained.The MoS2 / gold-mesoporous silica heterojunction material provided by the application has excellent near-infrared absorption, photothermal conversion and odor removal performance, and the preparation process is simple and efficient.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of mesoporous silica-based core-shell heterojunction material, in-situ synthesis method and application in smart wear, photo-thermal conversion and processing of odor removal textile, belong to material preparation and application technical field, BACKGROUND

[0002] Mesoporous silica (mSiO2) material has high specific surface area, strong adsorption, controllable structure, good biocompatibility and easy to modify surface, etc., has been widely used in catalysis, adsorption and carrier loading fields in recent years (see literature: Chem. Eng. J. 2023, 457 , 141263). Dendritic mesoporous silica material has a unique central radial pore structure, which is beneficial for the transfer of reactants along the central radial pore and can enhance the contact reaction with internal load or active sites (see literature: Science 2004, 306 , 5701). Using mesoporous silica as a carrier material, in-situ synthesis of noble metal nanoparticles (Au, Ag, Pt) in mesoporous silica cavities can effectively solve the problems of small-scale agglomeration and sintering of noble metal nanoparticles (see literature: Nano Lett. 2019, 19 , 1512).

[0003] In recent years, transition metal molybdenum disulfide (MoS2) has attracted widespread attention in the field of catalysis and energy conversion due to its good performance in solar energy utilization. Molybdenum sulfide (MoS2) is a typical transition metal disulfide, due to its large specific surface area and narrow band gap, it is used as a cocatalyst to improve the separation and migration efficiency of photo-induced electron-hole pairs and improve the light harvesting ability. However, the two-dimensional sheet material of molybdenum sulfide is prone to stacking when integrated with textiles, which greatly reduces the performance of the integrated material, and the limited photoelectron properties greatly hinder the application in the field of intelligent textiles. SUMMARY

[0004] The present application provides a kind of molybdenum sulfide / gold-mesoporous silica heterojunction material with core-shell structure and preparation method, the material not only has excellent photo-thermal conversion performance, but also has odor removal ability;The design of nanospherical core-shell structure effectively solves the stacking integration problem of material and textile, and can be applied to energy conversion, intelligent wear and home textile field.

[0005] The technical solution to achieve the purpose of the present application is to provide a preparation method of a mesoporous silica-based core-shell heterojunction material, comprising the following steps:

[0006] (1) mesoporous silica and cetyltrimethylammonium bromide are added to ultrapure water in a molar ratio of 1:1.0-1:3.0 to prepare a dispersion solution with a concentration of 5-10 g / L; the solution is heated and stirred in a water bath at 25-45 DEG C for 30-90 min to obtain a cationic surface-modified mesoporous silica solution;

[0007] (2) 0.02-0.06 M chloroauric acid solution is added to the cationic surface-modified mesoporous silica solution obtained in step (1), and the solution is continuously heated and stirred in a water bath at 25-45 DEG C for 3-5 h;

[0008] (3) 0.4-0.8 M sodium borohydride solution is added to the solution obtained in step (2), and the solution is continuously heated and stirred in a water bath at 25-45 DEG C for 30-90 min; after centrifugation, ultrapure water ultrasonic washing, and drying in a vacuum drying oven at 60-80 DEG C for 12-24 h, gold nanoparticle-loaded mesoporous silica is obtained;

[0009] (4) a precursor solution with a concentration of 5-10 g / L is prepared by mixing sodium molybdate dihydrate and thiourea in a molar ratio of 1:1-1:3; 0.5-2.0 mM gold-mesoporous silica obtained in step (3) is added, and the solution is ultrasonically treated for 10-30 min; 1-4 g / L polyethylene glycol 1000 is added, and the solution is stirred vigorously for 30-90 min;

[0010] (5) the solution obtained in step (4) is transferred to a polytetrafluoroethylene hydrothermal reactor, and hydrothermal reaction is carried out at a temperature of 180-220 DEG C for 12-18 h; after cooling, the precipitate is ultrasonically washed with deionized water and ethanol, centrifuged, and dried in a vacuum drying oven at 50-80 DEG C for 12-24 h to obtain a core-shell structured MoS / gold-mesoporous silica heterojunction material.

[0011] The technical scheme of the present application comprises a core-shell structured MoS / gold-mesoporous silica heterojunction material prepared according to the above preparation method.

[0012] The present application provides a core-shell structured MoS / gold-mesoporous silica heterojunction material, which is used to prepare a multifunctional fabric with near-infrared absorption, photothermal conversion, and odor removal. The steps are as follows: the core-shell structured MoS / gold-mesoporous silica is dissolved in deionized water to prepare a finishing solution with a concentration of 5-20 g / L; the fabric is placed in the finishing solution with a bath ratio of 1:30-1:50 and stirred for 10-20 h; after 2-5 times of padding-drying treatment, the fabric is dried in a vacuum drying oven at 50-80 DEG C for 12-24 h to obtain a multifunctional fabric with near-infrared absorption, photothermal conversion, and odor removal.

[0013] The fabric described in the application includes cotton fabric, silk fabric, wool fabric and chemical fiber fabric.

[0014] The multifunctional fabric provided by the application has near-infrared absorption, photothermal conversion and odor removal, the loading amount of molybdenum sulfide / gold-mesoporous silica on the fabric is 10-30 wt%, the surface temperature of the multifunctional fabric rises to 61.3 DEG C under the irradiation of 1 standard sunlight intensity, and the ammonia removal rate of the multifunctional fabric reaches 81.6% after 5 h of static treatment in a diluted 100 times ammonia atmosphere.

[0015] The principle of the application is that the surface of mesoporous silica is modified and grafted by a cationic surfactant, which is beneficial to the adsorption of gold source on the surface and pores of mesoporous silica by electrostatic force, then in-situ synthesis of gold nanoparticles in the pores of mesoporous silica is realized under the action of a reducing agent, and further, the epitaxial growth of molybdenum sulfide on the surface of mesoporous silica is realized by a hydrothermal method.

[0016] The application provides a porous structure silica with high specific surface area and high specific pore volume, realizes in-situ growth of gold nanoparticles on the surface and pores of mesoporous silica by grafting and modifying the surface of mesoporous silica, solves the problems of small size of gold nanoparticles and easy aggregation and sintering of gold nanoparticles, realizes the composite of the material and semiconductor material molybdenum sulfide by a simple one-step hydrothermal method in an epitaxial growth mode, and prepares a molybdenum sulfide / gold-mesoporous silica heterojunction material with a core-shell structure.

[0017] The application constructs a multi-component composite heterojunction material by an in-situ and epitaxial growth strategy, realizes the performance optimization and multifunctional advantages of a single material, and can further expand the engineering development of multifunctional material integrated textiles and the application in the field of intelligent textiles.

[0018] Compared with modern technologies, the application has the following beneficial effects:

[0019] 1. The in-situ synthesis and epitaxial growth method of the application prepares a molybdenum sulfide / gold-mesoporous silica core-shell heterojunction material with photothermal conversion performance and odor removal performance, the production process is simple and efficient, the product has high controllability, and the method is suitable for engineering production and application in the fields of personal thermal management and home textiles.

[0020] 2. The application uses high specific surface area dendritic mesoporous silica as a base material, realizes the composite of a core-shell multi-component heterojunction material, and realizes the multifunctionalization of nanomaterials in photothermal conversion and odor removal through controllable layer-by-layer growth.

[0021] 3. The molybdenum sulfide / gold-mesoporous silica core-shell heterostructure material provided by the present application, when combined with textiles, produces functional fabrics with excellent light-heat conversion performance and odor removal capacity, providing a new idea for the design of wearable energy conversion textiles. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 The scanning electron microscope (SEM) and transmission electron microscope (TEM) comparison diagrams of different products in the preparation process of the molybdenum sulfide / gold-mesoporous silica core-shell heterojunction material for the embodiments of the present application;

[0023] Figure 2 The X-ray diffraction (XRD) comparison diagram of different products in the preparation process of the molybdenum sulfide / gold-mesoporous silica core-shell heterojunction material for the embodiments of the present application;

[0024] Figure 3 The Raman spectrum (Roman) comparison diagram of different products in the preparation process of the molybdenum sulfide / gold-mesoporous silica core-shell heterojunction material for the embodiments of the present application;

[0025] Figure 4 The photothermal performance test result comparison diagram of different products under 808 nm infrared lamp irradiation in the preparation process of the molybdenum sulfide / gold-mesoporous silica core-shell heterojunction material for the embodiments of the present application;

[0026] Figure 5 The photothermal performance test comparison diagram of the molybdenum sulfide / gold-mesoporous silica core-shell heterojunction before and after loading on the cotton fabric for the embodiments of the present application;

[0027] Figure 6 The photothermal performance test result diagram of the molybdenum sulfide / gold-mesoporous silica core-shell heterojunction loaded on the cotton fabric under different sunlight intensities for the embodiments of the present application;

[0028] Figure 7 The ammonia gas removal performance test result diagram of the molybdenum sulfide / gold-mesoporous silica core-shell heterojunction loaded on the cotton fabric for the embodiments of the present application. DETAILED DESCRIPTION

[0029] The technical solutions will be further described by the following drawings and embodiments. Embodiment 1

[0030] Accurately weigh 0.1 g of mesoporous silica and 0.7 g of cetyltrimethylammonium bromide, dissolve them in 20 mL of ultrapure water, and heat and stir in a water bath at a temperature of 35℃ for 60 min to obtain a cationic surface-modified mesoporous silica solution.

[0031] The cation-modified mesoporous silica solution was added with 0.05 M chloroauric acid solution, and continuously heated and stirred in a water bath at 35 ℃ for 4 h; then 0.6 M sodium borohydride solution was added, and continuously heated and stirred in a water bath at 35 ℃ for 60 min, followed by centrifugation, ultrasonic washing with ultrapure water, and drying in a vacuum drying oven at 60 ℃ for 12 h, to obtain gold nanoparticle-loaded mesoporous silica.

[0032] Accurately weighed 0.3 g of sodium molybdate dihydrate and 0.45 g of thiourea were dissolved in 20 mL of deionized water, and 0.1 g of gold-mesoporous silica was added, ultrasonic treatment was performed for 20 min, and then 0.15 g of polyethylene glycol 1000 was added after the gold-mesoporous silica was completely dispersed, and the mixture was stirred vigorously for 60 min; then the mixture was subjected to hydrothermal reaction at 200 ℃ for 15 h, and after cooling, the precipitate was washed with deionized water and ethanol, centrifuged, and dried in a vacuum drying oven at 60 ℃ for 12 h, to obtain a core-shell structured molybdenum sulfide / gold-mesoporous silica heterojunction material.

[0033] Referring to the accompanying drawings Figure 1 FIGS. 1(a), 1(b) and 1(c) are scanning electron microscope (SEM) images and transmission electron microscope (TEM) images of mesoporous silica at different magnifications; FIGS. 1(d), 1(e) and 1(f) are SEM images and TEM images of gold nanoparticle-loaded mesoporous silica at different magnifications; and FIGS. 1(g), 1(h) and 1(i) are SEM images and TEM images of the core-shell structured molybdenum sulfide / gold-mesoporous silica heterojunction material at different magnifications. Figure 1 As can be seen from the comparison of the images in FIG. 1, the surface of the mesoporous silica is a dendritic porous structure; through cationic surface modification, the gold source is adsorbed in the pores of the mesoporous silica by electrostatic interaction between the cations and anions, and under the action of a reducing agent, gold nanoparticles are successfully synthesized in the pores of the mesoporous silica, with a diameter of 8-15 nm; and through hydrothermal growth, molybdenum sulfide is wrapped in the mesoporous silica, to obtain a core-shell structured molybdenum sulfide / gold-mesoporous silica heterojunction material.

[0034] Referring to the accompanying drawings Figure 2 FIG. 2 is an X-ray diffraction (XRD) pattern of the different products in the preparation of the molybdenum sulfide / gold-mesoporous silica core-shell heterojunction material of the present embodiment; and compared with the standard PDF card of molybdenum sulfide, the results confirm the successful preparation of the molybdenum sulfide / gold-mesoporous silica core-shell heterojunction material.

[0035] Referring to the accompanying drawings Figure 3Raman spectra of different products in the preparation of the molybdenum sulfide / gold-mesoporous silica core-shell heterojunction material of the present embodiment; the results further confirm the preparation of the molybdenum sulfide / gold-mesoporous silica core-shell heterojunction material.

[0036] See the accompanying Figure 4 The photothermal performance of different products in the preparation of the molybdenum sulfide / gold-mesoporous silica core-shell heterojunction material of the present embodiment under 808 nm infrared lamp irradiation; (a) is a comparison of the photothermal performance of different materials under the same power density; (b) is a comparison of the photothermal performance of the molybdenum sulfide / gold-mesoporous silica core-shell heterojunction under different power densities; under 808 nm infrared lamp irradiation, the molybdenum sulfide / gold-mesoporous silica exhibits excellent photothermal performance, and the temperature can rise to 120.6 ℃ when the power density is 0.372 W / cm2. Example 2

[0037] The molybdenum sulfide / gold-mesoporous silica core-shell heterojunction material prepared in Example 1 was configured into a finishing solution with a molybdenum sulfide / gold-mesoporous silica concentration of 10 g / L, and a cotton knitted fabric with a size of 10x10 cm 2 was placed in the finishing solution and stirred for 12 h, then padded and baked, and the operation was repeated twice, and then dried in a 60 ℃ vacuum drying oven for 12 h to obtain a cotton knitted fabric with near-infrared absorption and photothermal conversion.

[0038] The prepared core-shell structure molybdenum sulfide / gold-mesoporous silica heterojunction material exhibits excellent near-infrared absorption and photothermal conversion performance, and under 808 nm infrared lamp irradiation with a power density of 0.372 W / cm2, the temperature can rise to 120.6 ℃; after being loaded on the cotton knitted fabric, under 1 standard solar intensity irradiation, the temperature can rise to 61.3 ℃, and at the same time, the ammonia removal capacity is 81.6 %.

[0039] See the accompanying Figure 5 The photothermal performance of the molybdenum sulfide / gold-mesoporous silica core-shell heterojunction material prepared in the present embodiment under simulated sunlight irradiation; (a) is a comparison of the photothermal performance of different loaded fabrics under the same power density; (b) is a comparison of the photothermal performance of the molybdenum sulfide / gold-mesoporous silica core-shell heterojunction material loaded on the cotton knitted fabric under different power densities; after the molybdenum sulfide / gold-mesoporous silica is loaded on the cotton fabric, the fabric exhibits excellent photothermal performance, and the temperature of the molybdenum sulfide / gold-mesoporous silica cotton knitted fabric can rise to 67.2 ℃, compared with 29.7 ℃ of the pure cotton knitted fabric.

[0040] See the accompanying Figure 6The photo-thermal response of the molybdenum sulfide / gold-mesoporous silica core-shell heterojunction material prepared in this embodiment and loaded on cotton knitted fabric under simulated sunlight irradiation; the results confirmed that the molybdenum sulfide / gold-mesoporous silica cotton knitted fabric surface had excellent photo-thermal response under different power density simulated sunlight irradiation, and the fabric temperature rose to 61.3 ℃ under 1 standard sunlight intensity irradiation.

[0041] See the attached Figure 7 The ammonia removal performance of the molybdenum sulfide / gold-mesoporous silica core-shell heterojunction material prepared in this embodiment and loaded on cotton knitted fabric; the results showed that the molybdenum sulfide / gold-mesoporous silica cotton knitted fabric had an ammonia removal rate of 81.6% after 5 h. Example 3

[0042] Accurately weigh 0.05 g of mesoporous silica and 0.45 g of cetyltrimethylammonium bromide into 20 mL of ultrapure water, and heat and stir in a water bath at a temperature of 30 ℃ for 30 min to obtain a cationic surface-modified mesoporous silica solution.

[0043] Add 0.03 M of chloroauric acid solution to the cationic modified mesoporous silica solution, and continuously heat and stir in a water bath at a temperature of 30 ℃ for 3 h; then add 0.4 M of sodium borohydride solution, and continuously heat and stir in a water bath at a temperature of 30 ℃ for 30 min, then centrifuge, ultrapure water ultrasonic washing, and then placed in a 60 ℃ vacuum drying oven for drying for 12 h to obtain gold nanoparticle loaded mesoporous silica.

[0044] Accurately weigh 0.15 g of sodium molybdate dihydrate and 0.3 g of thiourea into 20 mL of deionized water, and add 0.05 g of gold-mesoporous silica, ultrasonic treatment for 20 min, then add 0.05 g of polyethylene glycol 1000 after the gold-mesoporous silica is completely dispersed, and stir vigorously for 60 min; then hydrothermal reaction at a temperature of 180 ℃ for 18 h, cool, and then ultrasonic washing, centrifugation with deionized water and ethanol, and then placed in a 60 ℃ vacuum drying oven for drying for 12 h to obtain the core-shell structured molybdenum sulfide / gold-mesoporous silica heterojunction material.

[0045] Prepare a finishing solution of molybdenum sulfide / gold-mesoporous silica with a concentration of 15 g / L, take a cotton knitted fabric with a size of 10×10 cm 2 in the finishing solution and stir for 10 h, then pad, bake, repeat the operation 2 times, and then place in a 60 ℃ vacuum drying oven for drying for 12 h to obtain a cotton knitted fabric with near-infrared absorption and photo-thermal conversion. Example 4

[0046] Accurately weigh 0.15 g of mesoporous silica and 0.9 g of cetyltrimethylammonium bromide into 20 mL of ultrapure water, and heat and stir in a water bath at 40 ℃ for 90 min to obtain a cationic surface-modified mesoporous silica solution.

[0047] Add 0.06 M chloroauric acid solution to the cationic modified mesoporous silica solution, and continue to heat and stir in a water bath at 40 ℃ for 5 h; then add 0.8 M sodium borohydride solution, and continue to heat and stir in a water bath at 40 ℃ for 90 min, then centrifuge, ultrasonic wash with ultrapure water, and then dry in a 60 ℃ vacuum drying oven for 12 h to obtain gold nanoparticle-loaded mesoporous silica.

[0048] Accurately weigh 0.45 g of sodium molybdate dihydrate and 0.7 g of thiourea into 20 mL of deionized water, and add 0.15 g of gold-mesoporous silica, ultrasonic treatment for 20 min, then add 0.2 g of polyethylene glycol 1000 after the gold-mesoporous silica is completely dispersed, and stir vigorously for 60 min; then hydrothermal reaction at 220 ℃ for 12 h, after cooling, ultrasonic washing, centrifugation with deionized water and ethanol, and then drying in a 60 ℃ vacuum drying oven for 12 h to obtain a core-shell structured molybdenum sulfide / gold-mesoporous silica heterojunction material.

[0049] Prepare a finishing solution of molybdenum sulfide / gold-mesoporous silica with a concentration of 8 g / L, and take a cotton knitted fabric with a size of 10×10 cm 2 and place it in the finishing solution for stirring for 15 h, then pad, bake, repeat the operation twice, and then dry in a 60 ℃ vacuum drying oven for 12 h to obtain a cotton knitted fabric with near-infrared absorption and photothermal conversion.

Claims

1. A method for preparing a mesoporous silica-based core-shell heterojunction material, characterized by The method comprises the following steps: (1) mesoporous silica and cetyltrimethylammonium bromide are added into ultrapure water at a molar ratio of 1:1.0-1:3.0 to prepare a dispersion solution with a concentration of 5-10 g / L; the solution is heated and stirred in a water bath at 25-45℃ for 30-90 min to obtain a cationic surface-modified mesoporous silica solution; (2) 0.02-0.06 M chloroauric acid solution is added to the cationic surface-modified mesoporous silica solution obtained in step (1), and the solution is continuously heated and stirred in a water bath at 25-45℃ for 3-5 h; (3) 0.4-0.8 M sodium borohydride solution is added to the solution obtained in step (2), and the solution is continuously heated and stirred in a water bath at 25-45℃ for 30-90 min; after centrifugation, ultrapure water ultrasonic washing, and drying in a vacuum drying oven at 60-80℃ for 12-24 h, gold nanoparticle-loaded mesoporous silica is obtained; (4) a precursor solution is prepared by mixing sodium molybdate dihydrate and thiourea at a molar ratio of 1:1-1:3 to obtain a solution with a concentration of 5-10 g / L; 0.5-2.0 mM gold-mesoporous silica obtained in step (3) is added, and the solution is ultrasonically treated for 10-30 min; 1-4 g / L polyethylene glycol 1000 is added, and the solution is stirred vigorously for 30-90 min; (5) the solution obtained in step (4) is transferred to a polytetrafluoroethylene hydrothermal reactor, and hydrothermal reaction is carried out at a temperature of 180-220℃ for 12-18 h; after cooling, the precipitate is washed with deionized water and ethanol, centrifuged, and dried in a vacuum drying oven at 50-80℃ for 12-24 h to obtain a core-shell structured molybdenum sulfide / gold-mesoporous silica heterojunction material.

2. The core-shell structured molybdenum sulfide / gold-mesoporous silica heterojunction material obtained by the method of claim 1.

3. Use of a core-shell structured molybdenum sulfide / gold-mesoporous silica heterojunction material according to claim 2, characterized in that The method for preparing multifunctional fabric with near-infrared absorption, photothermal conversion and odor removal comprises the following steps: dissolving the core-shell structured molybdenum sulfide / gold-mesoporous silica in deionized water to prepare a finishing solution with a concentration of 5-20 g / L; the fabric is placed in the finishing solution with a bath ratio of 1:30-1:50 and stirred for 10-20 h; after 2-5 times of padding-drying treatment, the fabric is dried in a vacuum drying oven at 50-80℃ for 12-24 h to obtain multifunctional fabric with near-infrared absorption, photothermal conversion and odor removal.

4. Use of a core-shell structured molybdenum sulfide / gold-mesoporous silica heterojunction material according to claim 3, characterized in that: The fabric includes cotton fabric, silk fabric, wool fabric and chemical fiber fabric.

5. Use of a core-shell structured molybdenum sulfide / gold-mesoporous silica heterojunction material according to claim 3, characterized in that: The loading amount of molybdenum sulfide / gold-mesoporous silica on the fabric is 10-30 wt%.

6. Use of a core-shell structured molybdenum sulfide / gold-mesoporous silica heterojunction material according to claim 3, characterized in that: Under the irradiation of 1 standard solar intensity, the surface temperature of the multifunctional fabric rises to 61.3℃.

7. Use of a core-shell structured molybdenum sulfide / gold-mesoporous silica heterojunction material according to claim 3, characterized in that: After standing in an ammonia atmosphere diluted by 100 times for 5 h, the ammonia removal rate of the multifunctional fabric reaches 81.6%.

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