阅读说明：本技术 用于气体检测的纳米复合敏感膜及其制备方法 (Nano composite sensitive film for gas detection and preparation method thereof ) 是由 邢晓波 薛盛 王天赐 谷文韬 陈明玉 王海燕 吴家隐 李宗宝 冯爽 于 2019-09-06 设计创作，主要内容包括：本发明公开一种用于气体检测的纳米复合敏感膜及其制备方法。该方法包括：提供透明衬底；在所述透明衬底上制作形成透明固定层；在所述透明固定层上制作形成敏感材料层,其中所述敏感材料层中包括量子点材料、金属纳米材料和具有负电性的微纳米透光材料。该敏感膜包括：透明衬底；透明固定层,设置于所述透明衬底上；敏感材料层,设置于所述透明固定层上,其中所述敏感材料层中包括量子点材料、金属纳米材料和具有负电性的微纳米透光材料。在制备过程中加入具有负电性的微纳米透光材料,有效地避免了量子点和金属纳米粒子的团聚问题,有利于提高量子点的活性和荧光强度。制成的敏感膜具有灵敏度高、稳定性好、寿命长、便于携带和操作等诸多优势。(the invention discloses a nano composite sensitive film for gas detection and a preparation method thereof. The method comprises the following steps: providing a transparent substrate; manufacturing and forming a transparent fixed layer on the transparent substrate; and manufacturing and forming a sensitive material layer on the transparent fixed layer, wherein the sensitive material layer comprises a quantum dot material, a metal nano material and a micro-nano light-transmitting material with electronegativity. The sensitive film comprises: a transparent substrate; a transparent fixed layer disposed on the transparent substrate; and the sensitive material layer is arranged on the transparent fixed layer, and comprises a quantum dot material, a metal nano material and a micro-nano light-transmitting material with electronegativity. The preparation method has the advantages that the electronegative micro-nano light-transmitting material is added in the preparation process, so that the problem of agglomeration of quantum dots and metal nanoparticles is effectively solved, and the activity and the fluorescence intensity of the quantum dots are improved. The prepared sensitive membrane has the advantages of high sensitivity, good stability, long service life, convenience in carrying and operation and the like.)

1. a method for preparing a nano composite sensitive film for gas detection is characterized by comprising the following steps:

Providing a transparent substrate (10);

Forming a transparent fixed layer (20) on the transparent substrate (10);

And manufacturing and forming a sensitive material layer (30) on the transparent fixed layer (20), wherein the sensitive material layer (40) comprises a quantum dot material, a metal nano material and a micro-nano light-transmitting material with electronegativity.

2. The method for preparing a nanocomposite sensor film for gas detection according to claim 1, wherein the method for forming a transparent fixed layer (20) on the substrate (10) comprises:

forming a polyvinyl alcohol layer (21) on the transparent substrate (10);

And manufacturing and forming a silicon dioxide array layer (22) on the polyvinyl alcohol layer (21) to form a transparent fixed layer (20).

3. The method for preparing the nanocomposite sensitive film for gas detection according to claim 2, wherein the silica array layer (22) is a single-layer array layer, and the material of the silica array layer (22) is silica spheres with a diameter of 1 μm to 999 μm.

4. The method for preparing the nanocomposite sensitive film for gas detection according to claim 3, wherein the micro-nano light-transmitting material with electronegativity is a fumed silica material, and the method further comprises:

Preparing a fumed silica solution;

Adding a quantum dot material into the fumed silica solution to form a mixed solution;

and adding a metal nano material into the mixed solution to form a sensitive material solution.

5. The method for preparing a nanocomposite sensor film for gas detection according to claim 4, wherein the method for forming the sensor material layer (30) on the silicon dioxide array layer (22) comprises:

and coating the sensitive material solution on the silicon dioxide array layer (22) and carrying out drying treatment to form a sensitive material layer (30).

6. The method for preparing the nanocomposite sensor film for gas detection according to claim 5, wherein the solution of the sensing material is coated on the silicon dioxide array layer (22) by spin coating, wherein the spin coating speed is 50r/s ~ 300 r/s.

7. The method for preparing the nanocomposite sensing membrane for gas detection according to claim 4, wherein the ambient temperature of the drying process is 273.15K ~ 303.15K, and the time of the drying process is more than 1 hour.

8. The method for preparing the nanocomposite sensing film for gas detection according to claim 1 or 4, wherein the diameter range of the quantum dot material is 1nm ~ 20nm, the diameter range of the metal nanomaterial is 10nm ~ 30nm, and the diameter range of the micro-nano light-transmitting material with electronegativity is 1nm ~ 999 nm.

9. the method of claim 1, wherein the difference between the excitation wavelength and the fluorescence wavelength of the quantum dot material is greater than 1 nm.

10. A nanocomposite, sensitive membrane for gas detection, comprising:

A transparent substrate (10);

A transparent fixing layer (20) disposed on the transparent substrate (10);

The sensitive material layer (30) is arranged on the transparent fixed layer (20), wherein the sensitive material layer (30) comprises a quantum dot material, a metal nano material and a micro-nano light-transmitting material with electronegativity.

Technical Field

the invention belongs to the technical field of gas detection, and particularly relates to a nano composite sensitive film for gas detection and a preparation method thereof.

Background

Formaldehyde (HCHO), a common indoor air pollutant, acts as a "possible human carcinogen" and poses a serious threat to human health and the environment. Studies have shown that formaldehyde exposure for 30 minutes allows concentrations of only 0.08 ppm. The National Institute for Occupational Safety and Health (NIOSH) has set 0.016ppm as the maximum long-term contact limit, and the world health organization has determined an exposure limit of 0.08ppm for 30 min. Therefore, it is necessary to monitor the concentration of formaldehyde timely and accurately. However, many conventional formaldehyde detection methods have disadvantages in cost, operation and accuracy,

Selective detection materials and efficient sensing structures have been extensively studied in order to achieve better performance. Quantum dots, which are the main components of Fluorescent Inorganic Nanoparticles (FINPs), have been expanded in recent years to many fields such as sensing, fluorescent imaging applications, microarrays, etc. due to their unique optical properties. Researchers have noted that localized surface plasmon resonance of rare metals can effectively enhance the fluorescence of quantum dots. Due to the problems of difficult film formation of the quantum dots, easy agglomeration of metal nanoparticles and the like, the research on the application of the metal particle surface plasma resonance enhanced quantum dot fluorescence has many difficulties.

Disclosure of Invention

(I) technical problems to be solved by the invention

The technical problem solved by the invention is as follows: how to overcome the problem that the quantum dots and the metal nano particles are easy to agglomerate so as to improve the fluorescence efficiency of the quantum dots.

(II) the technical scheme adopted by the invention

in order to solve the technical problems, the invention adopts the following technical scheme:

A method for preparing a nano composite sensitive membrane for gas detection comprises the following steps:

providing a transparent substrate;

Manufacturing and forming a transparent fixed layer on the transparent substrate;

And manufacturing and forming a sensitive material layer on the transparent fixed layer, wherein the sensitive material layer comprises a quantum dot material, a metal nano material and a micro-nano light-transmitting material with electronegativity.

Preferably, the method for forming the transparent fixed layer on the substrate comprises the following steps:

Manufacturing and forming a polyvinyl alcohol layer on the transparent substrate;

And manufacturing and forming a silicon dioxide array layer on the polyvinyl alcohol layer to form a transparent fixed layer.

preferably, the silicon dioxide array layer is a single-layer array layer, and the material of the silicon dioxide array layer is silicon dioxide spheres with the diameter of 1-999 μm.

Preferably, the micro-nano light-transmitting material with electronegativity is a fumed silica material, wherein the preparation method further comprises the following steps:

preparing a fumed silica solution;

Adding a quantum dot material into the fumed silica solution to form a mixed solution;

And adding a metal nano material into the mixed solution to form a sensitive material solution.

Preferably, the method for forming the sensitive material layer on the silicon dioxide array layer comprises the following steps:

And coating the sensitive material solution on the silicon dioxide array layer, and drying to form a sensitive material layer.

Preferably, the sensitive material solution is coated on the silicon dioxide array layer by adopting a spin coating mode, wherein the spin coating speed is 50r/s ~ 300r/s and 300 r/s.

Preferably, the ambient temperature of the drying treatment is 273.15K ~ 303.15K, and the time of the drying treatment is more than 1 hour.

Preferably, the diameter range of the quantum dot material is 1nm ~ 20nm, the diameter range of the metal nano material is 10nm ~ 30nm, and the diameter range of the electronegative micro-nano transparent material is 1nm ~ 999 nm.

Preferably, the difference between the excitation light wavelength and the fluorescence wavelength of the quantum dot material is greater than 1 nm.

The invention also provides a nano composite sensitive film for gas detection, which comprises the following components:

A transparent substrate;

a transparent fixed layer disposed on the transparent substrate;

and the sensitive material layer is arranged on the transparent fixed layer, and comprises a quantum dot material, a metal nano material and a micro-nano light-transmitting material with electronegativity.

(III) advantageous effects

The invention discloses a nano composite sensitive film for gas detection and a preparation method thereof, compared with the prior art, the nano composite sensitive film has the following advantages and beneficial effects:

The gas phase silicon dioxide material is added in the preparation process, so that the problem of agglomeration of the quantum dots and the metal nano particles can be effectively avoided, and the activity and the fluorescence intensity of the quantum dots can be improved. The prepared sensitive membrane can effectively detect the specificity of gas through the change of fluorescence, has the advantages of high sensitivity, good stability, long service life, convenience in carrying and operation and the like, and has wide application prospect in the fields of families, industry, environmental monitoring and the like.

Drawings

Fig. 1 is a schematic structural diagram of a nanocomposite sensing film for gas detection according to a first embodiment of the invention.

Fig. 2 is a flow chart of a method for preparing a nanocomposite sensing film for gas detection according to a first embodiment of the invention.

Fig. 3 is a TEM representation of a sensitive material of example two of the present invention.

Fig. 4 is a SEM characterization of the nanocomposite sensitive film according to the present invention.

FIG. 5 is a graph comparing the data of the change in fluorescence intensity before and after the addition of fumed silica to the sensing material according to the present invention.

FIG. 6 is a graph comparing fluorescence intensity changes before and after adding metal nanoparticles to the sensitive material according to the present invention.

FIG. 7 is a graph of data for fluorescence intensity of the present invention at 30ms integration time at various temperatures.

FIG. 8 is a graph of data for fluorescence intensity of the present invention at 30ms integration time under different humidities.

FIG. 9 is a graph showing the response data of the fluorescence intensity of the present invention at a formaldehyde concentration of 1 ppm at an integration time of 30 ms.

FIG. 10 is a graph showing the data of the fluorescence intensity of the present invention when the integration time is 30ms, in which formaldehyde and nitrogen gas are repeatedly introduced.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.