CN113218864B - Preparation method of nano material modified metal organic framework film and application of nano material modified metal organic framework film to sensor - Google Patents
Preparation method of nano material modified metal organic framework film and application of nano material modified metal organic framework film to sensor Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 75
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
- 230000003287 optical effect Effects 0.000 claims abstract description 7
- 239000010408 film Substances 0.000 claims abstract 6
- 239000010409 thin film Substances 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 239000007789 gas Substances 0.000 claims description 42
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 30
- 238000005507 spraying Methods 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 21
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 21
- 239000000758 substrate Substances 0.000 claims description 21
- 238000001514 detection method Methods 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 8
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- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 238000011010 flushing procedure Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
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- 239000000203 mixture Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- VHKFFPOTSWQHPK-UHFFFAOYSA-N C(C)O.C1(=CC(=CC(=C1)C(=O)O)C(=O)O)C(=O)O Chemical compound C(C)O.C1(=CC(=CC(=C1)C(=O)O)C(=O)O)C(=O)O VHKFFPOTSWQHPK-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 230000000007 visual effect Effects 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- GZTBKEOTCAVWNJ-UHFFFAOYSA-L C(C)O.C(C)(=O)[O-].[Cu+2].C(C)(=O)[O-] Chemical compound C(C)O.C(C)(=O)[O-].[Cu+2].C(C)(=O)[O-] GZTBKEOTCAVWNJ-UHFFFAOYSA-L 0.000 claims 2
- 238000004140 cleaning Methods 0.000 claims 1
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- 239000013307 optical fiber Substances 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 11
- 238000001179 sorption measurement Methods 0.000 abstract description 7
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- 238000012986 modification Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 31
- 239000000463 material Substances 0.000 description 24
- 239000013148 Cu-BTC MOF Substances 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 14
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 12
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- 238000004381 surface treatment Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000012491 analyte Substances 0.000 description 2
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- 239000001257 hydrogen Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 mass Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000007783 nanoporous material Substances 0.000 description 2
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 238000013528 artificial neural network Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
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- 239000003039 volatile agent Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
The invention relates to a preparation method of a nano material modified metal organic framework film and application thereof to a sensor, which realizes selective sensing identification and high sensing sensitivity of a MOFs film Fabry-Perot resonant cavity to gas. Firstly, synthesizing a nano material with controllable structure size, adding the nano material into a MOFs film by using a layer-by-layer assembly method, realizing the functional modification of the MOFs film, improving the optical property and the specific adsorption capacity of the MOFs@nanomaterials film, and realizing the high sensitivity and the selectivity of the sensor. In a word, the method has the characteristics of simplicity, stability, multiple functions, wide applicability and the like, and the MOFs-based Fabry-perot thin film sensor obtained by the method has good gas sensitivity and selectivity.
Description
Technical Field
The invention belongs to the field of optical communication technology and sensing, and particularly relates to a preparation method of a nanomaterial modified metal organic frame film and application of the nanomaterial modified metal organic frame film to a sensor.
Background
The sensing technology, the computer technology, the communication technology and the information technology are three main posts, which relate to the micro-machinery, the micro-electronics technology, the computer technology, the signal processing technology, the circuit, the system, the neural network technology, the fuzzy control theory and other comprehensive technologies, are applied to various fields (such as intelligent home, agriculture, medical treatment, military, space exploration and other fields) related to national economy and national defense scientific research, and are one of the basic and strategic industries of national economy. The sensor is a carrier of a sensing technology, and detects and senses external signals, physical conditions (such as light, heat, temperature, humidity and the like) or chemical stimulus, and converts detected information into electronic signals to be displayed at an output end. Over decades of development, sensors have penetrated extremely wide areas such as industrial production, environmental protection, medical diagnostics, biotechnology, and the like. The data show that the sensing market of China still keeps growing in 2019, the whole market scale reaches 2188.8 hundred million yuan, and the same ratio is increased by 12.7%. In the future, along with implementation of strategies such as industrial Internet, intelligent manufacturing, artificial intelligence and the like, the market scale of 2021 is expected to reach 2951.8 hundred million yuan, and the speed is expected to reach 17.6%.
Gas sensors have been widely used to monitor various gases and small molecule volatiles as an important branch in the direction of sensor application. The gas sensor mainly comprises a gas sensor and a conversion element, wherein the gas sensor is a part which can be directly sensed or correspondingly measured in the sensor, and the conversion element is a part which can be used for converting the sensed or responded measured part of the sensor into an electric signal suitable for transmission or measurement. In recent years, with the electronic development of national defense technology weapons, the aggravation of environmental pollution, the frequent occurrence of safety accidents, the importance of food safety, the progress of medical diagnosis and the like, a wide development space and opportunity are provided for the development of gas sensors. The gas sensor can prevent and check toxic gas and alarm, detect the room effect gas such as nitrogen and sulfur, detect the concentration of ethanol gas in the expired air of a driver, detect the freshness of perishable foods such as meat and the like, and diagnose some diseases by checking the components and the concentration of expired air. However, the conventional gas sensor faces the problems of few sensing types, small selectivity, low sensitivity, high requirements on working environment and the like of the gas sensor in the face of more and more special signals and environments. Therefore, the development of high-performance gas-sensitive materials, advanced preparation processes and novel sensing devices has important significance.
Metal-organic framework Materials (MOFs) are nano-porous materials formed by self-assembling Metal ions and organic ligands through coordination bonds, and the MOFs not only have a pore structure similar to the rule of zeolite molecular sieves, but also have the characteristics of higher specific surface area and porosity than the traditional porous materials, and simultaneously have the characteristics of designable composition structure, pore size and the like. The MOFs nano porous material can analyze the components and the concentration of the detection object in a certain range, and can rapidly and selectively adsorb the organic small molecules and the gas detection object by utilizing the characteristic differences of the pore channel structure, the size, the chemical environment and the like. Notably, MOFs change their own properties after adsorption of the analyte, such as mass, crystal structure, electrical properties, optical properties, and the like. Therefore, by utilizing the specific physicochemical properties of MOFs, the MOFs are used as gas sensitive elements to construct a novel gas sensor, and high gas monitoring sensitivity and selectivity can be realized.
The MOFs-based Fabry-Perot resonant cavity uses MOFs film as a reflecting layer, external light is absorbed, transmitted and reflected repeatedly by the film after entering the MOFs film, and finally a plurality of parallel reflected lights are formed, and the light is tuned by coherent interference of the parallel lights. However, the prior art reports that Fabry-perot gas sensors for MOFs have low detection sensitivity for analytes and that selective sensing is difficult to achieve. Thus, it is desirable that the gas sensitive material be composited with other functional materials to synergistically enhance sensing performance.
Disclosure of Invention
The invention solves the technical problems that: the invention relates to a preparation method of a nano material modified metal organic framework film and application of the nano material modified metal organic framework film to a sensor, in order to solve the problems that the existing gas sensor has low detection sensitivity to an analyte and is difficult to realize selective sensing.
The technical scheme of the invention is as follows: the preparation method of the nano material modified metal organic framework film comprises the following steps:
step 1: preparing a nano material: comprises the following substeps:
step 1.1: mixing and stirring the precursor compound and deionized water to obtain a solid, and then filtering and washing, wherein the volumes of the precursor compound and deionized water are respectively 10-20mL and 90-180mL;
step 1.2: stirring and mixing the solid filtered and washed in the step 1 with ammonium hydroxide, transferring the mixture into a hydrothermal kettle, and heating at constant temperature to obtain a nano material; centrifuging the obtained nano material at 13000-17000rpm to remove larger particles and agglomerates; wherein the heating temperature is constant temperature heating ammonium hydroxide aqueous solution with the volume of 2.5-4mL;
step 2: selecting a specific substrate material according to the need and carrying out surface treatment;
step 3: and (3) using a layer-by-layer assembly method, circularly spraying 1-10mM of metal salt (copper acetate, copper nitrate, zinc acetate, zinc nitrate and the like), 0.1-1mM of organic ligand (trimesic acid) ethanol solution on the surface of a substrate material according to the sequence of metal and organic solution, wherein the spraying time of the metal solution and the organic solution is respectively 10-20s, and washing a sample with ethanol solvent in each circulation gap to obtain the MOFs film.
The invention further adopts the technical scheme that: the substrate material in the step 1 is silicon wafer, quartz, glass or flexible material.
The invention further adopts the technical scheme that: the surface treatment in the step 1 means that the substrate is sequentially and respectively ultrasonically cleaned in 20-50mL of isopropanol, acetone and isopropanol for 10-30min, and then treated by oxygen ion for 3-5min after being dried by nitrogen.
The invention further adopts the technical scheme that: and (3) obtaining the MOFs film with specific thickness and refractive index by controlling the spraying times.
The invention further adopts the technical scheme that: the preparation method of the nanomaterial modified metal organic framework film gas sensor is characterized by comprising the following steps of:
step 1: according to the bragg diffraction formula: mλ=2nd, where n represents the refractive index of the mofs@nanomaterials film and d represents the thickness of the mofs@nanomaterials film; obtaining film thicknesses and refractive indexes corresponding to different reflection wavelengths;
step 2: selecting a specific substrate material according to the need and carrying out surface treatment;
step 3: and (3) circularly spraying 1-10mM of metal salt, 0.1-1mM of organic ligand and 0.0125-1.25mM of functional nano material ethanol solution on the surface of a substrate material according to the sequence of metal, organic and nano material solutions, and flushing a sample with ethanol solvent in each circulation gap to obtain the MOFs@nanomaterials film, wherein the spraying time of the metal solution, the organic solution and the nano material solution is respectively 10-20s.
The invention further adopts the technical scheme that: the substrate material in the step 2 is silicon wafer, quartz, glass or flexible material.
The invention further adopts the technical scheme that: the surface treatment in the step 2 means that the substrate is sequentially and respectively ultrasonically cleaned in 20-50mL of isopropanol, acetone and isopropanol for 10-30min, and oxygen plasma is used for treating for 3-5min after nitrogen is blown dry.
The invention further adopts the technical scheme that: and (3) by controlling the spraying times, obtaining the MOFs film modified by the nano material with specific thickness and refractive index, and using an Atomic Force Microscope (AFM) and an elliptical polarization spectrometer to characterize the surface roughness and thickness of the film.
The invention further adopts the technical scheme that: and (3) repeating the process of the step 3 for 100 times to obtain the MOFs@nanomatriles structure sensor.
Effects of the invention
The invention has the technical effects that: the method provided by the invention is simple to prepare and high in applicability, and compared with an unmodified metal-organic framework film, the gas sensor obtained by the method has better sensing sensitivity and selectivity. By adding uniformly dispersed functional nano materials into MOFs film, the characteristic of MOFs porous film is utilized, and the specific interaction between the surface physicochemical property of the nano materials and the object to be detected is improved, so that a MOFs (MOFs@nanomatriles) based Fabry-Prot gas sensor modified by the nano materials is constructed, and the detection sensitivity and selectivity of the gas detection object can be effectively improved. The MOFs@nanomaterials-based gas-sensitive material prepared by the method can be used as an optical feedback material of a Fabry-Perot resonant cavity, and can provide theoretical basis and technical support for development of an advanced nano sensor.
Drawings
FIG. 1 schematic diagram of the sensing of a gas detection object by a functional nanomaterial-modified MOFs-based Fabry-Perot sensor
FIG. 2 MOFs@TiO 2 Variation curve of film thickness and refractive index with cycle number
FIG. 3 morphological effects on MOFs film before and after functional nanoparticle addition: (a) AFM topography of 40 MOFs (b) 40 MOFs@TiO 2 AFM topography of (c)
FIG. 4 SEM cross-section thickness analysis of MOFs based Fabry-perot resonator: (a) 40 cycles of MOFs film and (b) 40 cycles of MOFs@TiO 2 Film and method for producing the same
FIG. 5 HKUST-1-based Fabry-perot sensor (a) with MOFs@TiO 2 Sensing curve of the base Fabry-perot sensor (b) for methanol
Detailed Description
Referring to fig. 1 to 5, the technical scheme of the invention comprises the following contents:
1. preparing nano material with good dispersibility in ethanol solution, and using TiO 2 For example, the method comprises the following steps:
step 1: mixing and stirring isopropanol and deionized water for 1 hour to obtain a white solid, and then filtering and washing with deionized water, wherein the volumes of titanium isopropoxide and deionized water are respectively 10-20mL and 90-180mL;
step 2: and (3) stirring and mixing the solid filtered and washed in the step (1) with 0.6mol/L ammonium hydroxide, transferring the mixture into a hydrothermal kettle, and heating at constant temperature to obtain the nano material. Centrifuging the obtained nano material at 13000-17000rpm to remove larger particles and agglomerates; wherein the heating temperature is 120 ℃, the constant temperature time is 3 hours, and the volume of the ammonium hydroxide aqueous solution is 2.5-4mL.
2. The preparation of the metal organic framework film comprises the following steps:
step 1: selecting a specific substrate material (such as silicon wafer, quartz, glass and flexible material) and performing surface treatment;
step 2: and (3) sequentially and circularly spraying a metal salt and an organic ligand solution on the surface of the substrate material by using a layer-by-layer assembly method through spraying equipment, and washing a sample with a solvent in each circulation gap to remove non-coordinated metal ions or organic ligands, thereby obtaining the uniform and compact MOFs film with a flat surface and controllable thickness.
The substrate silicon wafer is sequentially and respectively ultrasonically cleaned in isopropanol, acetone and isopropanol for 10-30min, and then treated by oxygen plasma for 3-5min after being dried by nitrogen.
The preparation method of the MOFs film comprises the following steps: taking the classical MOFs material HKUST-1 as an example, 1-10mM copper acetate (Cu (OAc) was first prepared 2 ) And 0.1-1mM of trimesic acid (BTC) ethanol solution, and circularly spraying the solution on the surface of the substrate material for 10-20s according to the sequence of metal and organic solution, and flushing the sample with ethanol solvent at each circulation gap to remove non-coordinated metal ions and organic ligands.
3. The preparation of the nanomaterial modified metal organic framework film gas sensor comprises the following steps:
step 1: according to the bragg diffraction formula: mλ=2nd, where n represents the refractive index of the mofs@nanomaterials film and d represents the thickness of the mofs@nanomaterials film. Obtaining film thicknesses and refractive indexes corresponding to different reflection wavelengths;
step 2: selecting a specific substrate material (such as silicon wafer, quartz, glass and flexible material) and performing surface treatment; the substrate silicon wafer is sequentially and respectively ultrasonically cleaned in isopropanol, acetone and isopropanol for 10-30min, and then treated by oxygen plasma for 3-5min after being dried by nitrogen.
Step 3: and (3) sequentially and circularly spraying the metal salt, the organic ligand and the nano material solution on the surface of the substrate material by using a layer-by-layer assembly method through spraying equipment, and flushing a sample with a solvent in each circulation gap to remove non-coordinated metal ions, organic ligands and nano materials. And (3) by controlling the spraying times, obtaining the MOFs film modified by the nano material with specific thickness and refractive index.
The preparation method of the MOFs@nanomatriles film comprises the following steps: first, 1-10mM copper acetate (Cu (OAc)) was prepared 2 ) And 0.1-1mM of trimesic acid (BTC) and 0.10125-1.25mM of functional nano material ethanol solution, spraying the three solutions according to the sequence of metal, organic and nano material solutions for 10-20s, and flushing each spraying gap with ethanol to remove uncomplexed metal ions, organic ligands and redundant nano particles.
In the preparation method of the MOFs@nanomaterials film sensor, the spraying cycle number of the MOFs@nanomaterials film is 100.
To verify the improvement of sensitivity and selectivity of the modified nanomaterial, a classical MOFs material HKUST-1 is taken as an example to prepare the modified nanomaterial with MOFs@TiO 2 Structural multicomponent Fabry-perot sensor:
example 1:
a preparation method of MOFs-based Fabry-perot gas sensor comprises the following specific steps:
step 1: fabry-Perot resonators based on MOFs material HKUST-1 are based on the Bragg diffraction formula: mλ=2nd, where n represents the refractive index of HKUST-1 film and d represents the thickness of HKUST-1 film. The thickness and refractive index of the film corresponding to different reflection wavelengths are obtained, and theoretical basis is provided for subsequent experiments.
Step 2: firstly, a substrate silicon wafer is sequentially and respectively ultrasonically cleaned in isopropanol, acetone and isopropanol for 10-30min, and then is treated by oxygen plasma for 3-5min after being dried by nitrogen, so that the number of hydroxyl functional groups on the surface is increased, and the hydrophilicity of the silicon surface is improved.
Step 3: first, 500mL of 1-10mM copper acetate (Cu (OAc)) was prepared 2 ) Ethanol solution, 500mL,0.1-1mM trimesic acid (BTC) ethanol solution, spraying the two solutions in the order of metal and organic solution for 10-20s, and flushing each spraying gap with ethanol ensures sufficient coordination between reactants. Repeating the assembling steps 10-100 times, HKUST-1 film with specific thickness was prepared (as shown in FIG. 3a, AFM test shows that MOFs film has flat and compact surface and low roughness).
Step 4: in the preparation of the HKUST-1-based Fabry-Prorot sensor, according to the calculation result based on the Bragg formula, the HKUST-1 film with corresponding thickness and refractive index is assembled layer by layer on the processed substrate (as shown in figure 4a, SEM sectional view shows the thickness of the MOFs film after 40 spraying cycles) to obtain the modified HKUST-1-based Fabry-Prorot sensor based on the functional nano material.
Step 5: through setting up liquid evaporation plant, design and customization sensing cavity, at last through devices such as optic fibre with sensing signal change visual optical signal into, realize the sensing detection of different gases. 10 mu L of the solvent to be detected (methanol, ethanol and the like) is placed in a liquid evaporation device, and 100sccm of nitrogen is used for sending detection gas into a sensor chamber, so that high-precision detection of gas molecules is realized.
Example 2:
TiO (titanium dioxide) 2 Modified MOFs@TiO 2 The preparation method of the base Fabry-Perot gas sensor comprises the following specific steps:
step 1: 20mL of titanium isopropoxide was added dropwise to 36mL of deionized water with vigorous stirring. The solution was stirred for 1 hour and the resulting white solid was filtered and washed with deionized water. The remaining solid was mixed with 3.9ml of 0.6m ammonium hydroxide and transferred to a hydrothermal kettle and heated at 120 ℃ for 3 hours. Larger particles and agglomerates were removed at 17000rpm and dispersed in ethanol solution for use.
Step 2: HKUST-1@TiO 2 The base Fabry-perot resonator is based on the bragg diffraction formula: mλ=2nd, where n represents the refractive index of HKUST-1 film and d represents HKUST-1@tio 2 Thickness of the film. The thickness and refractive index of the film corresponding to different reflection wavelengths are obtained, and theoretical basis is provided for subsequent experiments. Wherein, as shown in FIG. 2, the abscissa represents the number of spraying cycles, and the ordinate represents the thickness of MOFs film measured by ellipsometer, and the result shows that the thickness and refractive index of MOFs film increase with the change of the number of spraying cycles. I.e. can pass throughControlling the spraying times of the MOFs film controls the thickness and the refractive index of the MOFs film.
Step 3: firstly, a substrate silicon wafer is sequentially and respectively ultrasonically cleaned in isopropanol, acetone and isopropanol for 10-30min, and then is treated by oxygen plasma for 3-5min after being dried by nitrogen, so that the number of hydroxyl functional groups on the surface is increased, and the hydrophilicity on the surface of the silicon is improved.
Step 4: first, 500mL of 1-10mM copper acetate (Cu (OAc)) was prepared 2 ) Ethanol solution, 500mL,0.1-1mM trimesic acid (BTC) ethanol solution, 500mL,0.0125-1.25mM TiO 2 And (3) spraying an ethanol solution, namely spraying the three solutions according to the sequence of the metal solution, the organic solution and the nano material solution for 10-20s, wherein each spraying gap is washed by ethanol to ensure that reactants can be fully coordinated. Repeating the assembling step 10-100 times to prepare HKUST-1@TiO with specific thickness 2 Film (as shown in FIG. 3b, AFM test showed MOFs@TiO 2 The surface of the film is flat and compact, and the roughness is lower).
Step 4: in HKUST-1@TiO 2 In the preparation of the base Fabry-Perot sensor, according to the calculation result based on the Bragg formula, HKUST-1@TiO with corresponding thickness and refractive index is formed on the processed substrate 2 The film is assembled layer by layer (as shown in figure 4b, SEM cross section shows that the thickness of MOFs@HKUST-1 film after 40 spraying cycles) to obtain the modified HKUST-1@TiO based on the functional nano material 2 A base Fabry-perot sensor.
Step 5: through setting up liquid evaporation plant, design and customization sensing cavity, at last through devices such as optic fibre with sensing signal change visual optical signal into, realize the sensing detection of different gases. 10 mu L of the solvent to be detected (methanol, ethanol and the like) is placed in a liquid evaporation device, and 100sccm of nitrogen is used for sending detection gas into a sensor chamber, so that high-precision detection of gas molecules is realized.
The resulting Fabry-perot sensor based on MOFs material HKUST-1 of examples 1,2 and its sensing curve for methanol are shown in FIG. 5. Wherein, the abscissa represents wavelength, the ordinate represents reflection peak intensity, the black curve is the curve before sensing, and the gray curve is the change curve after methanol adsorption. The results show that the utility model is solidThe Fabry-perot sensors based on MOFs in example 1 and example 2 each have a higher sensing sensitivity for methanol, wherein the start response time of the methanol sensing curve in example 1 is 9.8s, and the methanol sensing start response time in example 2 is 2.0s, indicating a faster sensing speed in example 2. In addition, comparing the sensing performance of the two, the red shift distance of the peak position in example 1 is shorter, namely the response performance to methanol is weaker, but the functional nano particle TiO is added 2 After that, as a large number of hydroxyl groups are arranged on the surface of the titanium oxide, hydrogen bond interaction can be directly generated with methanol, the specific adsorption of sensing gas is realized, the pre-adsorption amount of the methanol is increased, and the selective sensing of analytes is realized. Thus the response to methanol increases substantially and the spectrum shows an increase in the red-shift distance of the curve. The reason is that the titanium oxide surface has a large number of hydroxyl groups, can directly generate hydrogen bond interaction with methanol, has the specific adsorption of sensing gas, increases the pre-adsorption amount of methanol, and realizes the selective sensing of analytes.
Claims (1)
1. TiO (titanium dioxide) 2 Modified MOFs@TiO 2 A selective sensing application of a base Fabry-perot gas sensor to methanol, characterized by: first preparing the TiO 2 Modified MOFs@TiO 2 A base Fabry-perot gas sensor; secondly, a liquid evaporation device is built, a sensing chamber is designed and customized, 10 mu L of methanol is placed into the liquid evaporation device, and 100sccm of nitrogen is used for sending detection gas into the sensing chamber; finally, converting the sensing signal into a visual optical signal through an optical fiber device, so as to realize the detection of high-precision gas molecules;
the TiO 2 Modified MOFs@TiO 2 The base Fabry-perot gas sensor is prepared by the following method:
step 1: dropwise adding titanium isopropoxide into deionized water under intense stirring, filtering and washing the white solid obtained by stirring with deionized water, stirring and mixing the filtered and washed solid with ammonium hydroxide, transferring the mixture into a hydrothermal kettle, heating at constant temperature, and centrifuging to remove larger particles and agglomerates to obtain TiO 2 Nanomaterial, tiO 2 Dispersing nano material in ethanol solution to obtain TiO 2 An ethanol solution;
step 2: respectively ultrasonically cleaning a substrate silicon wafer in isopropanol, acetone and isopropanol for 10-30min in sequence, drying by nitrogen, treating by oxygen plasma for 3-5min, increasing the number of hydroxyl functional groups on the surface of the silicon wafer, and improving the hydrophilicity on the surface of the silicon wafer;
step 3: preparing 1-10 copper acetate ethanol solution mM, 0.1-1mM trimesic acid ethanol solution and 0.0125-1.25mM TiO obtained in step 1 2 An ethanol solution; according to copper acetate ethanol solution, trimesic acid ethanol solution and TiO 2 Spraying the three solutions on the treated substrate sequentially for 10-20s, and flushing each spraying gap with ethanol to ensure that reactants can be fully coordinated; repeating the spraying assembly step for 10-100 times to prepare MOFs@TiO with specific thickness 2 Thin film, and MOFs@TiO with corresponding thickness and refractive index according to calculated result based on Bragg formula 2 The films are assembled layer by layer to obtain TiO 2 Modified MOFs@TiO 2 A base Fabry-perot gas sensor.
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