CN116539676B - Sensor based on metal phthalocyanine MOFs nano-sphere array with multistage mesoporous structure, and preparation method and application thereof - Google Patents
Sensor based on metal phthalocyanine MOFs nano-sphere array with multistage mesoporous structure, and preparation method and application thereof Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 61
- 239000002184 metal Substances 0.000 title claims abstract description 61
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 39
- 239000002077 nanosphere Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 28
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 28
- ROWKJAVDOGWPAT-UHFFFAOYSA-N Acetoin Chemical compound CC(O)C(C)=O ROWKJAVDOGWPAT-UHFFFAOYSA-N 0.000 claims abstract description 22
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- 239000000463 material Substances 0.000 claims abstract description 14
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- 238000006243 chemical reaction Methods 0.000 claims description 10
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- -1 (tetrazole) terephthalic acid Chemical compound 0.000 claims description 8
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-Me3C6H3 Natural products CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910021332 silicide Inorganic materials 0.000 claims description 8
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims description 8
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- 239000005977 Ethylene Substances 0.000 claims description 7
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 7
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- 150000003839 salts Chemical class 0.000 claims description 7
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical group C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
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- 229910000077 silane Inorganic materials 0.000 claims description 4
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012790 adhesive layer Substances 0.000 claims description 3
- 238000011161 development Methods 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 238000007781 pre-processing Methods 0.000 claims description 3
- 230000008961 swelling Effects 0.000 claims description 3
- YLAQGFWMVOQAGR-UHFFFAOYSA-N 2,5-bis(3-carboxyanilino)terephthalic acid Chemical compound C1=CC(=CC(=C1)NC2=CC(=C(C=C2C(=O)O)NC3=CC=CC(=C3)C(=O)O)C(=O)O)C(=O)O YLAQGFWMVOQAGR-UHFFFAOYSA-N 0.000 claims description 2
- WIOZZYWDYUOMAY-UHFFFAOYSA-N 2,5-diaminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=C(N)C=C1C(O)=O WIOZZYWDYUOMAY-UHFFFAOYSA-N 0.000 claims description 2
- LIIJDSZUAOXJLM-UHFFFAOYSA-J C(=O)(O)C1=C(O[Zn](OC2=C(C=CC=C2)C(=O)O)(OC2=C(C=CC=C2)C(=O)O)OC2=C(C=CC=C2)C(=O)O)C=CC=C1 Chemical group C(=O)(O)C1=C(O[Zn](OC2=C(C=CC=C2)C(=O)O)(OC2=C(C=CC=C2)C(=O)O)OC2=C(C=CC=C2)C(=O)O)C=CC=C1 LIIJDSZUAOXJLM-UHFFFAOYSA-J 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000003491 array Methods 0.000 claims description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000001087 glyceryl triacetate Substances 0.000 claims description 2
- 235000013773 glyceryl triacetate Nutrition 0.000 claims description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
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- 239000002052 molecular layer Substances 0.000 claims description 2
- MCTALTNNXRUUBZ-UHFFFAOYSA-N molport-000-691-724 Chemical compound [Pd+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MCTALTNNXRUUBZ-UHFFFAOYSA-N 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical group OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical group Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 2
- 229960002622 triacetin Drugs 0.000 claims description 2
- SSWMLKYBHOTWFA-UHFFFAOYSA-J tris[(2-hydroxybenzoyl)oxy]stannyl 2-hydroxybenzoate Chemical compound [Sn+4].Oc1ccccc1C([O-])=O.Oc1ccccc1C([O-])=O.Oc1ccccc1C([O-])=O.Oc1ccccc1C([O-])=O SSWMLKYBHOTWFA-UHFFFAOYSA-J 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 230000001105 regulatory effect Effects 0.000 description 10
- 238000001514 detection method Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 239000011540 sensing material Substances 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 5
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- 201000007270 liver cancer Diseases 0.000 description 4
- 208000014018 liver neoplasm Diseases 0.000 description 4
- 239000013337 mesoporous metal-organic framework Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000001338 self-assembly Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 201000011510 cancer Diseases 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
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- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
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- 229910021645 metal ion Inorganic materials 0.000 description 1
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- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Immunology (AREA)
- Biochemistry (AREA)
- Electrochemistry (AREA)
- Pathology (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
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- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention discloses a sensor based on a metal phthalocyanine MOFs nanosphere array with a multi-stage mesoporous structure, a preparation method and application thereof, wherein the sensor comprises a flexible substrate with a silicon dioxide dielectric layer, a flexible interdigital electrode and the metal phthalocyanine MOFs nanosphere array with the multi-stage mesoporous structure which are sequentially laminated, and the preparation method comprises the following steps: (1) preparing a flexible substrate with a silicon dioxide dielectric layer; (2) Preparing a flexible interdigital electrode on the surface of a flexible substrate with a silicon dioxide dielectric layer; (3) preparing metal phthalocyanine MOFs solution; (4) Immersing the material prepared in the step (2) into metal phthalocyanine MOFs solution, and sequentially carrying out spin coating treatment, steam-assisted crystallization treatment, template agent removal treatment and low-temperature plasma treatment. The sensor has good stability and high sensitivity, can be used for rapidly detecting at low temperature and can be used for detecting 3-hydroxy-2-butanone at ppb level.
Description
Technical Field
The invention relates to the technical field of sensors, in particular to a sensor based on a metal phthalocyanine MOFs nanosphere array with a multi-stage mesoporous structure, and a preparation method and application thereof.
Background
With the rapid development of smart medicine, the internet of things, smart phones, wearable equipment and the like, monitoring of specific Volatile Organic Compounds (VOCs) in expiration is taken as a novel noninvasive detection method with great potential, and has become a leading-edge research on diagnosis of serious diseases in the world today. The world governments have early discovery and early diagnosis of diseases, particularly cancer, as primary medical goals. Among them, liver cancer is hidden in onset, rapid in onset, and bad in prognosis, and is often called "king in cancer". Thus, a new urgent need exists for breath sensing detection techniques. Scientific researchers find that 3-hydroxy-2-butanone, styrene and decane can be used as potential markers of liver cancer, wherein 3-hydroxy-2-butanone is considered to be the most diagnostic value. The sensitivity and specificity of the markers for diagnosing liver cancer can reach 86.7% and 91.7%. However, the humidity of the expired breath sample is high (about 90% relative humidity), the number of interferents is large, and the content of disease-related gas markers in the expired breath of the human body is generally relatively low (the endogenous VOCs concentration is quantified between 1ppb and 500 ppb). At present, most of the exhalation detection sensing materials have low sensitivity and poor selectivity to extremely low-concentration gas, so that the design of efficient exhalation detection sensing devices becomes a field in which breakthrough is needed. Therefore, the sensing material which has the properties of humidity resistance and interference resistance and high selectivity for specific expiratory VOCs markers is researched under the conditions of high humidity and multiple interferences at room temperature, and is a technical problem which needs to be overcome at present.
Disclosure of Invention
The invention aims to: in order to solve the technical problems in the prior art, the invention aims to provide a sensor which has good selectivity and high sensitivity and can be rapidly detected under the conditions of low temperature and high humidity and is based on a metal phthalocyanine MOFs nanosphere array with a multi-level mesoporous structure, and also provides a preparation method of the sensor and application of the sensor in detecting ppb-level 3-hydroxy-2-butanone.
The technical scheme is as follows: the sensor based on the metal phthalocyanine MOFs nanosphere array with the multi-stage mesoporous structure comprises a flexible substrate with a silicon dioxide dielectric layer, a flexible interdigital electrode and the metal phthalocyanine MOFs nanosphere array with the multi-stage mesoporous structure, which are sequentially stacked.
Further, the size of the nanospheres is 100-200 nm, first-stage mesopores are uniformly distributed in the nanospheres, and the aperture of the first-stage mesopores is 3-7 nm; the nanosphere array forms uniformly distributed second-stage mesopores, and the aperture of the second-stage mesopores is 50-100 nm; the multi-stage mesoporous structure is beneficial to the diffusion and transmission of the gas to be measured; the array formed by the nanospheres is favorable for rapid transmission of carriers and plays an important role in improving the sensitivity, selectivity and response speed of the sensor.
The preparation method of the sensor based on the metal phthalocyanine MOFs nanosphere array with the multi-stage mesoporous structure comprises the following steps:
(1) Preparing a silicon dioxide dielectric layer on the surface of the flexible substrate to obtain the flexible substrate with the silicon dioxide dielectric layer;
(2) Preparing a flexible interdigital electrode on the surface of a flexible substrate with a silicon dioxide dielectric layer;
(3) Preparing metal phthalocyanine MOFs solution: firstly preparing a mixed solution of a surfactant serving as a template agent, an expanding agent and deionized water, then adding an organic acid and a compound containing ions with a Hofmeister effect, mixing, then adding a metal salt, a ligand and metal phthalocyanine, and stirring for reaction to obtain a metal phthalocyanine MOFs solution;
(4) Immersing the material prepared in the step (2) into the metal phthalocyanine MOFs solution prepared in the step (3), and sequentially performing spin coating treatment, steam-assisted crystallization treatment, template agent removal treatment and low-temperature plasma treatment to obtain the sensor.
Further, in the step (1), the step of preparing the silicon dioxide dielectric layer on the surface of the flexible substrate is as follows: firstly, preprocessing a flexible substrate, and then depositing a silicon dioxide dielectric layer on the surface of the flexible substrate through a deposition process; the parameters of the deposition process are as follows: the radio frequency is 10-20 kHz, the radio frequency power is 100-200W, the introduced gas comprises reaction gas and diluent gas, the reaction gas comprises silicide, oxygen and ethylene, the gas flow ratio of the silicide, the oxygen and the ethylene is 10-30:30-50:4-8, preferably 20:40:5, the flow of the silicide is 10-30 sccm, the silicide is silane, the diluent gas is argon, the gas flow of the argon is 400-1000 sccm, the reaction gas pressure is 5-50 Pa, the deposition temperature is 150-250 ℃, the deposition time is 5-10 min, and the thickness of the obtained silicon dioxide medium layer is 100-300 nm; the flexible substrate is ultrathin glass, polyimide film or polyvinylidene fluoride film.
Further, in the step (2), the step of preparing the flexible interdigital electrode is as follows: spin-coating an adhesive on the surface of the flexible substrate with the silicon dioxide dielectric layer, continuously spin-coating negative photoresist, carrying out second baking, exposing treatment, third baking and developing treatment, carrying out vacuum metal coating, and removing the photoresist to obtain the flexible interdigital electrode; the adhesive is hexamethyldisilazane, and spin coating parameters are as follows: the rotating speed is 3000-5000 rpm, the time is 20-40 seconds, and the parameters of the first drying are as follows: the temperature is 80-100 ℃ and the time is 2-4 minutes, the negative photoresist is JSR series negative photoresist, and the parameters of the second drying are as follows: the temperature is 100-120 ℃ and the time is 2-4 minutes; the parameters of the exposure process are: the light intensity is 2.4-8.4W/cm 2 The exposure time is 4-40 seconds; the parameters of the third drying are as follows: the temperature is 90-120 ℃ and the time is 2-4 minutes; the parameters of the development treatment are: spraying and developing by adopting JSR series developer, wherein the spraying time is 40-80 seconds; the photoresist is removed by the steps of: removing residual photoresist in NMP bath at 50-80deg.C for 3-7 hr, cleaning, and vacuum drying; the vacuum metal coating comprises the following steps: first depositing a Ti/TiN layer, depositing 20-40 nm of titanium metal and 40-60 nm of titanium nitride by using a low-temperature deposition mode, wherein titanium is used as an adhesive layer, titanium nitride is used as an auxiliary layer, and then depositing 40-120 nm of gold nano-layer.
Further, in the step (3), the surfactant is F127, P123 or PEO-PS-PEO, preferably PEO-PS-PEO, the swelling agent is 1,3, 5-trimethylbenzene, glyceryl triacetate or dioctyl phthalate, preferably 1,3, 5-trimethylbenzene, and the molar ratio of the swelling agent to the surfactant is 4.5-36.2, preferably 18:1.
Further, in the step (3), the organic acid is acetic acid, and the ion with the Hofmeister effect is perchlorate, nitrate or sulfate; the molar ratio of the organic acid to the compound containing ions having the Hofmeister effect for the catalytic reaction is 6.8:1-2, preferably 6.8:1.41.
Further, in the step (3), the metal salt is tungsten chloride, the ligand is 2, 5-diamino terephthalic acid, 2, 5-bis ((3-carboxyphenyl) amino) terephthalic acid or 2, 5-bis (tetrazole) terephthalic acid, the metal phthalocyanine is tetra (carboxyphenoxy) zinc phthalocyanine, tetra (carboxyphenoxy) palladium phthalocyanine, tetra (carboxyphenoxy) tin phthalocyanine or tetra (carboxyphenoxy) platinum phthalocyanine, the molar ratio of the metal salt, the ligand and the metal phthalocyanine is 1:0.3-0.5:0.1-0.3, preferably 1:0.44:0.2, the stirring reaction temperature is 35-55 ℃ and the stirring reaction time is 1.5-3 h.
Further, in the step (4), the spin-coating process includes: the relative humidity is 10-50%, the speed is 4000-6000 rpm, and the time is 30-60 s; the parameters of the steam-assisted crystallization treatment are as follows: the relative humidity is 85-95%, the temperature is 100-120 ℃, and the reaction time is 18-30 h; the parameters of the low-temperature plasma are as follows: the temperature is 0-15deg.C, the frequency is 40-60 KHz, the power is 100-120W, and the time is 5-7 min.
The invention relates to an application of a sensor based on a metal phthalocyanine MOFs nanosphere array with a multi-level mesoporous structure in detecting ppb-level 3-hydroxy-2-butanone.
The principle of the invention: in order to meet the requirements of improving the sensing detection performance in a high-humidity and multi-interference monitoring environment, the mesoporous metal organic framework material has controllable physical and chemical characteristics and excellent low-temperature film forming property, and has the characteristics of low manufacturing cost, high response speed, low detection cost, no need of high-temperature calcination for manufacturing devices and the like. The carrier mobility and the surface activity can be regulated and controlled by regulating the defect composition and the electron energy level structure of the mesoporous metal organic framework and modifying the surface ligand. In addition, the metal-organic framework is a porous inorganic-organic hybrid material with a periodic network structure, which is formed by self-assembly of metal ions and organic ligands, is a crystalline porous nano material, has the characteristics of adjustable pore diameter, large specific surface area, high porosity and the like, and can improve the sensitivity and selectivity of sensor detection. Further solves the defect of poor selectivity of the traditional gas-sensitive material, and is an ideal sensing material for preparing low-power consumption and high-performance breath detection sensing devices.
The invention reasonably introduces a multilevel mesoporous metal organic frame material with huge potential in the field of gas-sensitive sensing, designs a series of metal phthalocyanine MOFs sensing materials with brand new structures, and prepares an ultrasensitive high-selectivity sensing device. The metal phthalocyanine MOFs sensing material system is directly constructed by adopting a 'bottom-up' vapor-assisted crystallization method, micelle formation is generated by controlling interface electrostatic assembly at a molecular scale, micelle aggregation assembly is further induced, and the multistage mesoporous metal organic framework nanosphere array with strong moisture resistance and high sensitivity is constructed in situ. The structure and the performance of the mesoporous MOFs nanospheres are controllably regulated, and the moisture resistance and the anti-interference performance of the sensing device are improved, so that the ultrasensitive and rapid response to the ppb-level concentration 3-hydroxy-2-butanone gas at room temperature is realized.
The invention uses photoetching technology to manufacture flexible interdigital electrodes as a substrate for loading mesoporous metal organic frame nanosphere arrays. Preparing metal phthalocyanine MOFs precursor solution by a wet chemical one-step method, realizing volatilization-induced self-assembly by using a spin coating method, and constructing a self-assembly body by using metal salt and metal phthalocyanine as a binding unit by using Hofmeister special effect. The self-assembly is treated by a steam-assisted crystallization technology, and the ordering and crystallinity of the metal phthalocyanine MOFs pore structure are regulated. And the energy level structure of the MOFs material is further regulated by using a plasma surface functionalization technology, so that the surface interface defect distribution of the material is effectively regulated and controlled. The uniform dispersity and the ordered pore structure of the nanosphere array are improved, the electron transmission capability and the gas-sensitive activity are effectively improved, the problems of poor uniformity and large fluctuation of parameters of each device of the existing MOFs material are solved, and the high sensitivity and high selectivity of the sensing performance of the 3-hydroxy-2-butanone are realized.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: the invention constructs the metal organic frame nanosphere array based on multistage mesopores, and prepares the high-performance sensing device. The aperture of the nanosphere is adjustable, rapid transmission of carriers of the induction layer is facilitated, and the high-efficiency sensing device suitable for the multi-interference environment is developed. The gas-sensitive sensing test is carried out, the adjustment of a multi-stage structure and the matching of sensing performance are facilitated, the sensing characteristic of the sensor that the performance of ppb-level 3-hydroxy-2-butanone is adjustable is realized, and an exhalation diagnosis model of liver cancer is established.
Drawings
FIG. 1 is a field emission scanning electron microscope image of metal phthalocyanine MOFs nanospheres with a multi-stage mesoporous structure prepared in example 1 of the present invention;
FIG. 2 is a graph showing the response test of the sensor prepared in example 1 of the present invention to different concentrations of 3-hydroxy-2-butanone gas;
FIG. 3 is a graph showing the gas selectivity of the sensor according to example 1 of the present invention.
Detailed Description
The invention will be further described with reference to specific examples and figures.
Example 1: the sensor based on the metal phthalocyanine MOFs nanosphere array with the multi-stage mesoporous structure comprises a flexible substrate with a silicon dioxide dielectric layer, a flexible interdigital electrode and the metal phthalocyanine MOFs nanosphere array with the multi-stage mesoporous structure, wherein the flexible substrate, the flexible interdigital electrode and the metal phthalocyanine MOFs nanosphere array with the multi-stage mesoporous structure are sequentially stacked, the size of the nanospheres is 100-200 nm, first-stage mesopores are uniformly distributed in the nanospheres, and the aperture of the first-stage mesopores is 3-7 nm; the nanosphere array forms uniformly distributed second-stage mesopores, the pore diameter of the second-stage mesopores is 50-100 nm, and the preparation method comprises the following steps:
(1) Preparing a silicon dioxide dielectric layer on the surface of a polyimide film of a flexible substrate to obtain the polyimide film with the silicon dioxide dielectric layer, which comprises the following specific steps: firstly, preprocessing a polyimide film: washing polyimide film with deionized water, soaking in acetone for 10 min, ultrasonic cleaning in an ultrasonic cleaner with ethanol for 10 min, washing with deionized water, and oven drying; and then a silicon dioxide dielectric layer is deposited on the surface of the polyimide film through a deposition process: (2) Filling a polyimide film into a reaction cavity, enabling the surface of the polyimide film to face an inner electrode, vacuumizing the reaction cavity at a distance of 80 mm, pumping a vacuum chamber to 2.0 Pa, introducing reaction gas into the reaction cavity, wherein the flow ratio of silane to oxygen to ethylene is 20/40/5 sccm (argon is taken as diluent gas flow to be 500 sccm, ethylene is taken as buffer gas), the reaction air pressure is 40 Pa, inputting radio frequency power with the frequency of 13.56 MHz, the radio frequency power is 120W, adjusting the coating time or adjusting the flow of silane, ethylene, oxygen and argon, preparing a silicon dioxide dielectric layer with excellent structure and performance, controlling the temperature of the silicon dioxide dielectric layer to 200 ℃, depositing the film time to 7 min, controlling the thickness of the silicon dioxide dielectric layer to 200 nm, cooling the temperature of the reaction cavity to room temperature, and taking out to obtain the polyimide film with the silicon dioxide dielectric layer with the thickness of 100-300 nm;
(2) Preparing a flexible interdigital electrode on the surface of a polyimide film with a silicon dioxide dielectric layer: in order to improve the adhesive force between the photoresist and the polyimide film, the adhesive hexamethyldisilazane is spin-coated on a clean flexible substrate on a spin coater at a rotation speed of 5000 rpm for 30 s, the spin-coated polymer is glued to a thickness of 300 nm, the first drying is carried out, and the baking is carried out on a heating plate at 100 ℃ for 2 min; spin-coating JSR series negative photoresist on the surface of the adhesive, wherein the rotation speed is 4000 rpm, the spin-coating time is 30 s, baking for the second time is carried out, baking is carried out on a heating plate at 120 ℃ for 2 min, and exposure treatment is carried out: performing lithography on a mask aligner with a regulated light intensity of 6.4W/cm 2 The exposure time is 30 s, after exposure, the third baking is carried out, the heating baking is carried out on a heating plate at 110 ℃ for 2 min, a substrate is formed, the substrate is placed on a spin coater, spraying and developing are carried out on the substrate by using JSR series developer, the spraying time is 60 s, and then the developer is removed by washing with deionized water; vacuum evaporation of the metal layer is carried out: firstly depositing a Ti/TiN layer, firstly introducing argon to bombard a titanium target material, depositing a titanium film, then introducing argon and nitrogen to bombard the titanium target material, depositing a titanium nitride film, depositing 30 nm titanium metal and 50 nm titanium nitride by using a low-temperature deposition mode, taking titanium as an adhesive layer, taking titanium nitride as an auxiliary layer, and then depositing 100 nm gold nano-layersThe method comprises the steps of carrying out a first treatment on the surface of the And then removing the photoresist: removing residual photoresist 5 h in NMP bath at 70 ℃, cleaning, and vacuum drying to obtain a flexible interdigital electrode;
(3) Preparing metal phthalocyanine MOFs solution: 50 PEO-PS-PEO of mg was dissolved in 5 ml deionized water, then 1,3, 5-trimethylbenzene was added in a ratio of 1,3, 5-trimethylbenzene to PEO-PS-PEO of 18.1 to prepare a mixture, the mixture was kept stirring at 40℃for 30 minutes, and acetic acid (0.40 ml,6.8 mmol) and NaClO were added after cooling to room temperature 4 (200 mg,1.41 mmol) the mixture was further stirred to form a homogeneous solution; adding WCl again 6 (0.5 mmol), 2, 5-bis (tetrazole) terephthalic acid (0.22 mmol) and tetra (carboxyphenoxy) platinum phthalocyanine (0.01 mmol), and then stirring 2 h at 40 ℃ to obtain metal phthalocyanine MOFs solution;
(4) Immersing the material prepared in the step (2) into the metal phthalocyanine MOFs solution prepared in the step (3), and sequentially performing spin coating treatment, steam-assisted crystallization treatment, template removal treatment and low-temperature plasma treatment, wherein the method comprises the following steps of: the relative humidity in a spin coater is regulated to be 50%, the spin coating speed is 4500 rpm, metal phthalocyanine MOFs solution is spin coated on a flexible interdigital electrode, the spin coating time is 35 s, the metal phthalocyanine MOFs solution is then placed in a closed container, the relative humidity in the closed container is regulated to be 90%, the temperature of the closed container is regulated to be 100 ℃, the reaction time is 24 h, and the obtained material is washed by adopting a mode of washing with deionized water once and washing with N, N-dimethylformamide twice after the completion of the reaction; in order to remove the surfactant used as the template agent, the material is soaked in acetone at 60 ℃ for 2 days, the acetone is updated every day during the period, finally, the product is dried under vacuum at 60 ℃ overnight, finally, the material is treated by adopting low-temperature plasma surface functionalization, the temperature is 0-15 ℃, the frequency of a used plasma cleaning machine is 40 KHz, the power is 100W, and the plasma cleaning time is 5 min, so that the sensor is obtained.
The resulting sensor was characterized and tested and the results are shown in fig. 1-3.
As shown in fig. 1, a metal phthalocyanine MOFs nanosphere array with a multi-level mesoporous structure; the size of the nanospheres is between 100 and 200 and nm, and the nanospheres are tightly connected, so that the carrier transmission is facilitated. The gaps formed in the nanosphere array are beneficial to the transmission of the gas to be measured.
As shown in FIG. 2, the response of the sensor to different concentrations of 3-hydroxy-2-butanone gas was measured. The response values for 10 ppm, 5 ppm, 1000 ppb, 500 ppb, 200 ppb, 100 ppb and 50 ppb concentration gases were 598, 278, 120, 68, 49, 25 and 8, respectively.
As shown in fig. 3, the selectivity of the sensor for 12 VOCs gases at 5 ppm concentration showed excellent selectivity of the sensor.
Claims (8)
1. A sensor based on a metal phthalocyanine MOFs nanosphere array with a multi-stage mesoporous structure is characterized by comprising a flexible substrate with a silicon dioxide dielectric layer, a flexible interdigital electrode and a metal phthalocyanine MOFs nanosphere array with a multi-stage mesoporous structure which are sequentially stacked; the size of the nanospheres is 100-200 nm, first-stage mesopores are uniformly distributed in the nanospheres, and the aperture of the first-stage mesopores is 3-7 nm; the nanosphere array forms uniformly distributed second-stage mesopores, and the aperture of the second-stage mesopores is 50-100 nm; the preparation method of the sensor based on the metal phthalocyanine MOFs nanosphere array with the multi-stage mesoporous structure comprises the following steps of:
(1) Preparing a silicon dioxide dielectric layer on the surface of the flexible substrate to obtain the flexible substrate with the silicon dioxide dielectric layer;
(2) Preparing a flexible interdigital electrode on the surface of a flexible substrate with a silicon dioxide dielectric layer;
(3) Preparing metal phthalocyanine MOFs precursor solution: firstly preparing a mixed solution of a surfactant serving as a template agent, an expanding agent and deionized water, then adding an organic acid and a compound containing ions with a Hofmeister effect, mixing, then adding a metal salt, a ligand and metal phthalocyanine, and stirring for reaction to obtain a metal phthalocyanine MOFs precursor solution;
(4) Immersing the material prepared in the step (2) into the metal phthalocyanine MOFs precursor solution prepared in the step (3), and sequentially performing spin coating treatment, steam-assisted crystallization treatment, template agent removal treatment and low-temperature plasma treatment to obtain a sensor; in the step (3), the molar ratio of the expanding agent to the surfactant is 4.5-36.2:1; the molar ratio of the organic acid to the compound containing the Hofmeister specific counter ion is 6.8:1-2; the molar ratio of the metal salt to the ligand to the metal phthalocyanine is 1:0.3-0.5:0.1-0.3, the temperature of the stirring reaction is 35-55 ℃ and the time is 1.5-3 h.
2. The sensor of claim 1, wherein in step (1), the step of preparing a silicon dioxide dielectric layer on the surface of the flexible substrate comprises: firstly, preprocessing a flexible substrate, and then depositing a silicon dioxide dielectric layer on the surface of the flexible substrate through a deposition process; the parameters of the deposition process are as follows: the radio frequency is 10-20 kHz, the radio frequency power is 100-200W, the introduced gas comprises reaction gas and diluent gas, the reaction gas comprises silicide, oxygen and ethylene, the gas flow ratio of the silicide to the oxygen to the ethylene is 10-30:30-50:4-8, the flow of the silicide is 10-30 sccm, the silicide is silane, the diluent gas is argon, the gas flow of the argon is 400-1000 sccm, the reaction gas pressure is 5-50 Pa, the deposition temperature is 150-250 ℃, the deposition time is 5-10 min, and the thickness of the obtained silicon dioxide medium layer is 100-300 nm; the flexible substrate is ultrathin glass, polyimide film or polyvinylidene fluoride film.
3. The sensor of claim 1, wherein in step (2), the step of preparing the flexible interdigitated electrodes is: spin-coating an adhesive on the surface of the flexible substrate with the silicon dioxide dielectric layer, continuously spin-coating negative photoresist, carrying out second baking, exposing treatment, third baking and developing treatment, carrying out vacuum metal coating, and removing the photoresist to obtain the flexible interdigital electrode; the adhesive is hexamethyldisilazane, and spin coating parameters are as follows: the rotating speed is 3000-5000 rpm, the time is 20-40 seconds, and the parameters of the first drying are as follows: the temperature is 80-100 ℃ and the time is 2-4 minutes, the negative photoresist is JSR series negative photoresist, and the parameters of the second drying are as follows: the temperature is 100-120deg.C for a period of time2-4 minutes; the parameters of the exposure process are: the light intensity is 2.4-8.4W/cm 2 The exposure time is 4-40 seconds; the parameters of the third drying are as follows: the temperature is 90-120 ℃ and the time is 2-4 minutes; the parameters of the development treatment are: spraying and developing by adopting JSR series developer, wherein the spraying time is 40-80 seconds; the vacuum metal coating comprises the following steps: first depositing a Ti/TiN layer, depositing 20-40 nm of titanium metal and 40-60 nm of titanium nitride by using a low-temperature deposition mode, wherein titanium is used as an adhesive layer, titanium nitride is used as an auxiliary layer, and then depositing 40-120 nm of gold nano-layer.
4. The sensor of claim 1, wherein in step (3), the surfactant is F127, P123, or PEO-PS-PEO, and the swelling agent is 1,3, 5-trimethylbenzene, glyceryl triacetate, or dioctyl phthalate.
5. The sensor of claim 1, wherein in step (3), the organic acid is acetic acid and the ion having the hofmeister effect is perchlorate, nitrate, or sulfate.
6. The sensor of claim 1, wherein in step (3) the metal salt is tungsten chloride, the ligand is 2, 5-diamino terephthalic acid, 2, 5-bis ((3-carboxyphenyl) amino) terephthalic acid, or 2, 5-bis (tetrazole) terephthalic acid, and the metal phthalocyanine is tetra (carboxyphenoxy) zinc phthalocyanine, tetra (carboxyphenoxy) palladium phthalocyanine, tetra (carboxyphenoxy) tin phthalocyanine, or tetra (carboxyphenoxy) platinum phthalocyanine.
7. The sensor of claim 1, wherein in step (4), the spin-coating process parameters are: the relative humidity is 10-50%, the speed is 4000-6000 rpm, and the time is 30-60 s; the parameters of the steam-assisted crystallization treatment are as follows: the relative humidity is 85-95%, the temperature is 100-120 ℃, and the reaction time is 18-30 h; the parameters of the low-temperature plasma treatment are as follows: the temperature is 0-15deg.C, the frequency is 40-60 KHz, the power is 100-120W, and the time is 5-7 min.
8. Use of a sensor based on metal phthalocyanine MOFs nanosphere arrays with a multi-level mesoporous structure according to claim 1 for detecting ppb-level 3-hydroxy-2-butanone.
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