CN114686002A - MOX @ NH2-MOFs thin film material and preparation method and application thereof - Google Patents
MOX @ NH2-MOFs thin film material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 64
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 61
- 239000010409 thin film Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000010408 film Substances 0.000 claims abstract description 60
- 239000002360 explosive Substances 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 20
- 238000001514 detection method Methods 0.000 claims abstract description 12
- 230000001699 photocatalysis Effects 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 239000000758 substrate Substances 0.000 claims description 40
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 40
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims description 15
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002070 nanowire Substances 0.000 claims description 12
- 238000004729 solvothermal method Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002105 nanoparticle Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910052751 metal Chemical class 0.000 claims description 8
- 239000002184 metal Chemical class 0.000 claims description 8
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000013110 organic ligand Substances 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 238000003491 array Methods 0.000 claims description 3
- 239000013183 functionalized metal-organic framework Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000011895 specific detection Methods 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 238000012360 testing method Methods 0.000 abstract description 11
- 230000031700 light absorption Effects 0.000 abstract description 7
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 238000011896 sensitive detection Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 38
- 239000010936 titanium Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000007605 air drying Methods 0.000 description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000013207 UiO-66 Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- PSVSZBOMJGAVRS-UHFFFAOYSA-N 2,3-diaminoterephthalic acid Chemical compound NC1=C(N)C(C(O)=O)=CC=C1C(O)=O PSVSZBOMJGAVRS-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 3
- 239000013259 porous coordination polymer Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910052594 sapphire Inorganic materials 0.000 description 3
- 239000010980 sapphire Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 2
- 230000032900 absorption of visible light Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 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 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000013177 MIL-101 Substances 0.000 description 1
- 239000013178 MIL-101(Cr) Substances 0.000 description 1
- 239000013179 MIL-101(Fe) Substances 0.000 description 1
- 239000013206 MIL-53 Substances 0.000 description 1
- 239000013216 MIL-68 Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000001559 infrared map Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004094 preconcentration Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 229950002929 trinitrophenol Drugs 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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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
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Abstract
The invention discloses a MOX @ NH2-MOFs thin film material, preparation method and application thereof, NH2MOFs is uniformly and continuously coated on an MOX film with obvious photocatalytic activity, and the sensitivity of room-temperature gas-sensitive detection is improved by introducing an optically active free group by utilizing the good photocatalytic performance of MOX. By reacting MOX with NH2The MOFs is compounded, so that the light absorption range can be widened, electrons can be rapidly transferred into MOX, electron-hole pairs are effectively separated, the photocatalytic activity of the composite material is improved, and the existing chemical resistance based on metal oxide is overcomeThe bottleneck problem of low selectivity and low sensitivity of the room temperature test nitro-explosive is solved, and the high selectivity and high sensitivity rapid detection of the room temperature nitro-explosive atmosphere is realized.
Description
Technical Field
The invention relates to the field of functional material science and the field of gas-sensitive sensing materials, in particular to MOX @ NH2-MOFs thin film material and preparation method and application thereof.
Background
Explosives have irreplaceable effects in national defense safety, space application and engineering blasting, and meanwhile, the problems of environmental pollution caused by explosion of the explosives, terrorist attacks made by terrorists and the like are always concerned by the whole society. TNT, DNT, TNP, RDX and the like are important standard nitro explosives, the saturated vapor pressure at room temperature is very low, for example, the TNT is 9ppb, the DNT is 180ppb, the TNP is 0.97ppb, the RDX is 4.9ppt, and the low vapor pressure makes real-time online high-sensitivity detection of the atmosphere of a plurality of technologies and materials at room temperature difficult to realize. Therefore, it is very important to explore new materials capable of efficiently and rapidly detecting and measuring nitro explosives.
Due to the advantages of low price, long service life, easy batch preparation and the like, the chemical resistance type sensor based on the metal oxide has wide application prospect in the fields of breath diagnosis, intelligent home, traffic, air quality detection and the like. However, high operating temperature (> 200 ℃) and poor selectivity are two major bottleneck problems restricting the application of the MOX chemical resistance type gas sensor in the field. High temperatures in particular directly limit the detection of explosives. MOX (TiO)2ZnO or SnO2) As a main material of the chemical resistance type gas sensor, the material has the advantages of stable performance, easy preparation, low price, easy shape control and the like, and particularly has excellent photocatalytic performance, so that the material can realize room temperature sensing under the assistance of ultraviolet light. But because the specific surface area is low, the functionalization modification is difficult, the band gap is wide, and the electron-hole is easy to be rapidly compounded, the ultraviolet light can only be used for assistance in the actual detection, and the sensitivity is low and the selectivity is poor.
Metal-Organic Frameworks (MOFs), also known as Porous Coordination Polymers (PCPs), are crystalline porous coordination polymers with a regular network structure self-assembled from Metal ions or Metal clusters and Organic ligands. Due to its ultra-high porosity, high specific surface area, tailorable frames and rich topologies, the design of the structure has attracted more and more attention. And amino-functionalized MOFs (NH)2MOFs) then combines the MOFs material with amino functional groupsFor example, the band gap is regulated to have the absorption of visible light.
At present, due to NH2-MOFs materials need to be lattice matched to MOX, NH2Continuous epitaxial growth of MOFs on the surface of MOX micro-nano materials is difficult; most of NH2MOFs are non-conductive and electron holes generated by light excitation are easy to recombine, and the direct wrapping of the MOFs on MOX seriously influences the transmission of electric signals in the material; NH (NH)2The strong adsorption of MOFs to nitro explosives may cause difficulty in rapid recovery as room temperature sensors, and may not achieve ultra-rapid response and recovery of gas sensors. Thus, there is no disclosure of MOX @ NH at present2The MOFs thin film material is used for a chemical resistance type sensor to detect the atmosphere of the nitro explosive under the assistance of light.
Disclosure of Invention
In order to improve the technical problem, the invention provides MOX @ NH2-MOFs thin film material, NH2-MOFs are uniformly and continuously coated on MOX film, NH2The coating rate of the MOFs is 100%.
According to the invention, the MOX is a film with significant photocatalytic activity, comprising nanoparticles, an array of nanowires, for example TiO2Nanowires, ZnO and SnO2Preferably TiO2A nanowire.
According to the technical scheme of the invention, the particle size of the MOX material is 50-300nm, and the length of the MOX material is 1-4 mu m.
According to the invention, NH2The MOFs material may be NH2-MIL-125(Ti),NH2-UIO-66(Zr),NH2-MIL-101(Fe),NH2-MIL-101(Cr),NH2-MIL-101(Al),NH2-MIL-53(Al),NH2-MOF-508，NH2-CU3(BTC)2,Fe-MIL-88-NH2,MOF-5-NH2,NH2-MIL-68(In),UMCM-1-NH2Preferably NH2-MIL-125。
According to the technical scheme of the invention, the MOX @ NH2The MOFs thin film material is a uniform and continuous coated core-sheath structure，NH2-MOFs with adjustable bandgap, said NH2-the band gap of the MOFs is 1.3-3.2 eV; the band gap of the MOX is 3-3.2 eV. Reacting MOX with NH2-MOFs band gap matching, enabling them to have significant visible light absorption and photocatalytic activity; while NH having a high specific surface area and amino functions2-MOFs, enabling the selective pre-enrichment of Lewis acidic species.
The invention also provides MOX @ NH2The preparation method of the MOFs thin film material specifically comprises the following steps:
a. preparing a MOX film on a non-conductive substrate;
b. packaging NH outside the MOX film in the step a by adopting a seed crystal assisted solvothermal method2-MOFs Material preparation MOX @ NH2-MOFs thin film materials.
According to the technical scheme of the invention, the non-conductive substrate is AL2O3One or more of glass, sapphire and silicon chip substrate; is preferably AL2O3。
According to the technical scheme of the invention, in the step b, the temperature is 100-200 ℃ in the seed crystal assisted solvothermal method, and the solvothermal time is 24-96h, preferably 72 h.
According to the technical scheme of the invention, the packaging method in the step b comprises the following steps: adopting one of spin coating, dipping, pulling and in-situ growth methods to prepare NH2-the MOFs material is compounded on the MOX film; in situ growth is preferred.
According to the technical scheme of the invention, the MOX is TiO2(ii) a Said TiO in step a2The preparation method of the film comprises the following steps: dissolving tetra-n-butyl titanate in a first solvent, soaking the substrate in the first solvent, and calcining to prepare the substrate with the seed crystal layer; then putting the substrate with the seed crystal layer into a polytetrafluoroethylene mold, adding tetra-n-butyl titanate and a second solvent, heating and calcining to prepare TiO2A film. According to the technical scheme of the invention, the first solvent is ethanol.
According to the technical scheme of the invention, the second solvent is a mixture of hydrochloric acid and water; the volume ratio of the hydrochloric acid to the water is 1: 1.
According to the technical scheme of the invention, the calcining temperature is 430-460 ℃, preferably 450 ℃; the calcination time is 20-70 min.
According to the technical scheme of the invention, the MOX is SnO2(ii) a SnO described in step a2The preparation method of the film comprises the following steps: fully dissolving 3mmol of KBr in deionized water to obtain a first solution; 1mmol of SnCl4.5H2Fully dissolving O in acetic acid to obtain a second solution;
then mixing the first solution and the second solution, and adding 10ml of ethanol to obtain a third solution; filling the third solution into a polytetrafluoroethylene lining, adding a cut glass slide with the thickness of 1cm multiplied by 2cm, putting the lining into a steel sleeve, putting the lining into an oven at the temperature of 200 ℃, and reacting the solvent for 24 hours to obtain SnO consisting of nanowires2A film.
According to the technical scheme of the invention, after a third solution is prepared, Sn powder is added into the third solution to prepare a fourth solution, the third solution is filled into a polytetrafluoroethylene lining, a cut glass slide with the thickness of 1cm multiplied by 2cm is added, the lining is put into a steel sleeve and is put into an oven to react for 24 hours at the temperature of 200 ℃, and continuous SnO consisting of nano particles is obtained2The film with the thickness of 200-500nm can be used as a transparent device.
According to the technical scheme of the invention, amino functional metal organic framework (NH) is adopted in the step b2-MOFs) material is prepared by adopting a conventional preparation method in the prior art, and the preparation method comprises the following specific steps: dissolving organic ligand containing amino and metal salt in mixed solvent of anhydrous methanol and DMF, mixing uniformly, heating for reaction, drying, and preparing NH2-MOFs materials.
According to the technical scheme of the invention, the volume ratio of the anhydrous methanol to the DMF is (1-9): (9-1). Preferably 1: 9.
According to the technical scheme of the invention, the molar ratio of the organic ligand containing amino groups to the metal salt is (20-1): 1, preferably 1: 1.
According to the solution of the invention, the NH2Specific surface area of the MOFs material is 1000-3000m2 g-1The pore diameter is 0.2-2 nm.
According to the technical scheme of the invention, the heating temperature is 100-220 ℃; the heating time is 15-96 h; the drying temperature is 80-150 ℃, and the drying time is 12-48 h; preferably, drying is carried out at 80 ℃ for 12 h.
According to the technical scheme of the invention, the organic ligand for functionalizing the amino is diaminoterephthalic acid (NH)2-BDC), 2, 5-diaminoterephthalic acid ((NH)2)2-BDC), at least one of 2-amino-1, 4-benzenedicarboxylic Acid (ABDC)), preferably NH2-BDC。
According to the technical scheme of the invention, the metal In the metal salt is one or more of titanium (Ti), zirconium (Zr), iron (Fe), chromium (Cr), aluminum (Al), copper (Cu) or indium (In); preferably titanium (Ti) and zirconium (Zr); preferably, when the metal salt is a titanium (Ti) salt, it may be tetra-n-butyl titanate, titanium tetrachloride or titanium trichloride, preferably, tetra-n-butyl titanate; when the metal salt is a zirconium salt, it may be zirconium tetrachloride.
The invention also provides MOX @ NH2The preparation method of the MOFs thin film material for preparing the chemical resistance type sensor comprises the following specific steps:
at MOX @ NH2And fixedly connecting a conductive electrode on the MOFs thin film material, and connecting the conductive electrode with a power supply to prepare the chemical resistance type sensor.
According to the technical scheme of the invention, the method is specifically carried out at MOX @ NH2Two ends of the MOFs film material are fixedly connected with two leads, the MOFs film material is connected with a Gilbert cell, dry air is introduced, and the MOFs film material is aged for 12 hours under the voltage of 5V to prepare the chemical resistance type sensor. So as to reduce the defects of the material and improve the contact of the grain boundary, thereby improving the stability of the device.
The invention also provides application of the chemical resistance sensor, which is applied to detection of nitro explosive atmosphere, and the specific detection method comprises the following steps:
and applying voltage to the chemical resistance type sensor, placing the chemical resistance type sensor in the nitro explosive atmosphere, and detecting.
According to the technical scheme of the invention, the nitro explosive is TNT, DNT, PA, RDX or derivatives thereof.
According to the technical scheme of the invention, the detection temperature is normal temperature.
According to the technical scheme of the invention, the detection is carried out under visible light, and the wavelength of the visible light is 420-790 nm.
The invention has the beneficial effects that:
(1) the invention utilizes the good photocatalysis performance of MOX, and improves the sensitivity of room temperature gas-sensitive detection by introducing the optical active free radical.
(2) NH in the thin film material of the invention2The introduction of MOFs can increase the porosity and specific surface area of the material, thus increasing the pre-enrichment of very low concentrations of nitro-explosive vapours; the band gap of the material is adjusted by introducing an amino functional group, so that the material has visible light absorption, and MOX @ NH is allowed2MOFs also have high sensitivity in visible light. TNT, DNT, PA, RDX are all electron deficient materials due to the nitro functional group. And NH2The amino groups of the MOFs readily donate electrons, thereby enhancing the selective adsorption of the nitro-explosive atmosphere.
(3) The invention is prepared by mixing MOX and NH2The MOFs is compounded, so that the light absorption range can be widened, electrons can be rapidly transferred to MOX, electron-hole pairs are effectively separated, the photocatalytic activity of the composite material is improved, the bottleneck problem that the conventional chemical resistance type sensor based on metal oxide is low in selectivity and low in sensitivity when used for testing the nitro explosives at room temperature is solved, and the high-selectivity and high-sensitivity rapid detection of the atmosphere of the nitro explosives at room temperature is realized.
(4) Firstly, MOX @ NH2The MOFs composite material is used for a chemical resistance type sensor to detect the nitro explosives, provides a new possible material for the detection of the nitro explosives, and researches possible structure-activity relationships (as shown in figures 4 and 5) through theoretical calculation, in-situ XPS, IR test and the like, thereby providing powerful guidance for the detection of the following explosives. The introduction of amino functionalized MOFs brings selective enrichment and preconcentration on the nitro explosive atmosphere, high-sensitivity and high-selectivity response to the nitro explosive atmosphere is realized in real time on line, and the response value to 0.97ppb trinitrophenol can reach 174%.
Drawings
FIG. 1 shows TiO in example 12SEM image of nanowire array film;
FIG. 2 is SnO of example 22SEM image of nanowire array film;
FIG. 3 is SnO consisting of nanoparticles of example 32SEM images of continuous films:
FIG. 4 shows TiO in example 42@NH2IR map of MIL-125 film material;
FIG. 5 shows TiO in example 42@NH2-XPS test pattern of MIL-125 thin film material;
FIG. 6 shows TiO in example 42@NH2SEM picture of MIL-125;
FIG. 7 shows TiO in example 52@NH2-SEM picture of UIO-66;
FIG. 8 is a schematic diagram of the preparation of the MOX @ MOFs film and the atmosphere test of nitro-explosives under room temperature visible light in example 6;
FIG. 9 is a schematic view of an apparatus for testing explosives using the chemical resistance type sensor of example 6;
FIG. 10 shows TiO in example 62@NH2Response of MIL-125 to 0.97PA at ambient temperature-recovery curve.
Detailed Description
The materials of the present invention, methods of making the same, and uses thereof, are described in further detail below with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
TiO 22The preparation method of the film comprises the following steps:
dissolving tetrabutyl titanate in ethanol, and cleaningSoaking sapphire substrate in ethanol solution containing tetrabutyl titanate for 3 hr, directly taking out, washing with ethanol, air drying, calcining at 450 deg.C for 30min to obtain a layer of TiO2A seed layer substrate composed of nanoparticles. Fixing the substrate in a polytetrafluoroethylene lining with the surface facing downwards, mixing 6ml of hydrochloric acid with 6ml of deionized water, adding 0.4ml of tetra-n-butyl titanate, adding the tetra-n-butyl titanate and the polytetrafluoroethylene lining together, covering the lining tightly, putting the lining into a stainless steel autoclave, putting the autoclave into an oven, keeping the temperature at 150 ℃ for 4 hours, taking out the substrate, washing the substrate with ethanol, naturally drying the substrate in the air, calcining the substrate at 450 ℃ for 30 minutes to obtain the substrate made of TiO on the sapphire substrate2The SEM image of a thin film composed of nanowire arrays is shown in FIG. 1.
Example 2
SnO (stannic oxide)2The preparation method of the film comprises the following steps:
3mmol (357mg) of KBr was dissolved in 10ml of deionized water to obtain a first solution. 1mmol (350.6mg) of SnCl4.5H2O was dissolved in 60ml of acetic acid to obtain a second solution. The first and second solutions were then mixed and 10ml of ethanol was added to obtain a third solution. Filling the third solution into a polytetrafluoroethylene lining, adding a cut slide glass with the thickness of 1cm multiplied by 2cm, putting the lining into a steel sleeve, putting the lining into an oven at the temperature of 200 ℃, and reacting the solvent for 24 hours to obtain SnO2The film, SEM of which is shown in FIG. 2, is a continuous SnO consisting of nanowire arrays2The film is white, has good ultraviolet light absorption, has very obvious photoconduction under ultraviolet light, and has fast response speed.
Example 3
SnO (stannic oxide)2The preparation method of the film comprises the following steps:
3mmol (357mg) of KBr was dissolved in 10ml of deionized water to obtain a first solution. 1mmol (350.6mg) of SnCl4.5H2O was dissolved in 60ml of acetic acid to obtain a second solution. The first solution and the second solution were then mixed, and 10ml of ethanol was added to obtain a third solution. And adding 0.2mmol of Sn powder into the third solution to obtain a fourth solution.Filling the fourth solution into a polytetrafluoroethylene lining, adding a cut slide glass with the thickness of 1cm multiplied by 2cm, putting the lining into a steel sleeve, putting the lining into an oven at the temperature of 200 ℃, and reacting the solvent for 24 hours to obtain SnO2The SEM image of the film is shown in FIG. 3. As can be seen from fig. 3, after the Sn powder is added, the morphology changes from the nanowire array in example 2 to continuous dense nanoparticles. The color of the powder scraped from the substrate also changed from white in example 2 to yellowish in example 3. SnO in example 22There was no oxygen defect and almost no visible light absorption, and the band gap was 3 eV. Example 3 is an oxygen deficient SnO-x film with visible light absorption and a band gap of 2.6 eV. Moreover, the thickness of the film in the embodiment 3 is adjustable between 200-500nm, and the film can be made into a transparent electronic device.
Example 4
TiO 22@NH2-a method for preparing MIL-125 film material; the method comprises the following steps:
1. dissolving tetra-n-butyl titanate in ethanol, and then dissolving clean Al2O3Soaking the substrate in ethanol solution containing tetrabutyl titanate for 3 hr, directly taking out, washing with ethanol, air drying, calcining at 450 deg.C for 30min to obtain a layer of TiO2A seed layer composed of nanoparticles; fixing the substrate in a polytetrafluoroethylene lining with the surface facing downwards, mixing 6ml of hydrochloric acid with 6ml of deionized water, adding 0.4ml of tetra-n-butyl titanate, adding the hydrochloric acid and the deionized water into the polytetrafluoroethylene lining, covering the lining tightly, putting the lining into a stainless steel autoclave, putting the autoclave into an oven, keeping the temperature at 150 ℃ for 4 hours, taking out the substrate, washing the substrate with ethanol, naturally drying the substrate in the air, calcining the substrate at 450 ℃ for 30 minutes to obtain the Al-doped aluminum oxide grown on the substrate2O3TiO on substrate2A film.
2. 18ml of anhydrous DMF and 2ml of anhydrous methanol were mixed and 0.2172g of NH were added2BDC, after having completely dissolved it, a first mixed solution is prepared, the TiO of step 1 being added2Soaking the film into the first mixed solution, carrying out high-pressure solvothermal reaction on the film and the first mixed solution at the temperature of 150 ℃ for 12 hours, and taking out the film to obtain a ligand NH2-BDC modified TiO2A film. Mixing 18ml DMF and 2ml anhydrous methanol, adding 0.21ml tetrabutyl titanate to prepare a second mixed solution, and adding NH2-BDC modified TiO2Putting the film into the second mixed solution, carrying out high-pressure solvothermal reaction together, taking out the film after the reaction condition is 150 ℃ for 4 hours, and preparing NH2-MIL-125 seed modified TiO2A film.
3. 18ml of DMF and 2ml of solution are mixed and 0.2172g of NH are added2BDC and 0.21ml tetra-n-butyl titanate, to make a fourth mixed solution, NH from step 22-MIL-125 seed modified TiO2Soaking the film into the fourth mixed solution, carrying out high-pressure solvothermal reaction at 150 ℃ for 72 hours, and taking out to obtain TiO2@NH2-MIL-125(Ti)。NH2Uniformly and continuously coating MOFs on MOX film to prepare TiO2@NH2-MIL-125 thin film material; NH (NH)2The coating rate of the MOFs is 100%.
The NH2-MIL-125(Ti) has a bandgap of 2.6 eV; the band gap of MOX is 3.0eV, the two band gaps are matched, NH2MIL-125(Ti) has a significant absorption of visible light, NH under irradiation of visible light2Separation of electrons and holes of MIL-125(Ti), followed by electron transfer to TiO2The separation of photo-generated electron-hole pairs is well promoted.
Prepared TiO2@NH2The IR diagram of the MIL-125 film material is shown in FIG. 4;
prepared TiO2@NH2NH in MIL-125 film material2XPS test pattern for MIL-125 is shown in FIG. 5;
prepared TiO2@NH2SEM image of-MIL-125 thin film material is shown in FIG. 6.
Example 5
TiO 22@NH2-method for the synthesis of UIO-66 thin film material comprising the following steps:
1. dissolving tetra-n-butyl titanate in ethanol, and then dissolving clean Al2O3The substrate was immersed in an ethanol solution in which tetra-n-butyl titanate was dissolvedTaking out for 3h, washing with ethanol, air drying, calcining at 450 deg.C for 30min to obtain a layer of TiO2A seed layer composed of nanoparticles. Fixing the substrate inside a polytetrafluoroethylene lining with the surface facing downwards, mixing 6ml of hydrochloric acid with 6ml of deionized water, adding 0.4ml of tetra-n-butyl titanate, adding the tetra-n-butyl titanate and the hydrochloric acid into the polytetrafluoroethylene lining, covering the lining tightly, putting the lining into a stainless steel autoclave, putting the autoclave into an oven, keeping the temperature at 150 ℃ for 4 hours, taking out the substrate, washing the substrate with ethanol, naturally drying the substrate in the air, and calcining the substrate at 450 ℃ for 30 minutes to obtain Al2O3On a substrate made of TiO2A film.
2. 60ml of DMF and 0.19ml of H 20, then 1.029mmol of ZrCl is added4,0.77mmol H2ATA and 0.26mmol H2DTA, stirring for 10min at room temperature to thoroughly mix the DTA and the TiO in the step 12Soaking the film in the solution, carrying out high-pressure solvothermal reaction at 120 ℃ for 24h, and taking out to obtain TiO2@NH2UIO-66, SEM picture as shown in FIG. 7.
Example 6
TiO 22@NH2A method for detecting the atmosphere of nitro explosives by using a room temperature chemical resistance sensor by using MOFs thin film material, a preparation diagram of MOX @ MOFs thin film and a test diagram of the atmosphere of nitro explosives under room temperature visible light, wherein the preparation diagram is shown in the specification; the MOX @ MOFs film is TiO2@NH2-MIL-125 film;
the method specifically comprises the following steps:
1. dissolving tetra-n-butyl titanate in ethanol, and then dissolving clean Al2O3Soaking the substrate in ethanol solution containing tetrabutyl titanate for 3 hr, directly taking out, washing with ethanol, air drying, calcining at 450 deg.C for 30min to obtain a layer of TiO2A seed layer composed of nanoparticles. Then fixing the substrate in a polytetrafluoroethylene lining with the surface facing downwards, mixing 6ml of hydrochloric acid with 6ml of deionized water, adding 0.4ml of tetra-n-butyl titanate, adding the mixture into the polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a stainless steel autoclave, putting the autoclave into an oven, keeping the temperature at 150 ℃ for 4 hours, taking out the substrate,washing with ethanol, air drying, calcining at 450 deg.C for 30min to obtain the product2O3TiO on substrate2A film.
2. 18ml of anhydrous DMF and 2ml of anhydrous methanol solution were mixed and 0.2172g of NH were added2BDC, after complete dissolution, the TiO of step 12The film is immersed into the solution, and then the film and the solution are subjected to a high-pressure solvothermal reaction, and the film is taken out after the reaction condition is 150 ℃ for 12 hours. Mixing 18ml of DMF and 2ml of anhydrous methanol solution, adding 0.21ml of tetra-n-butyl titanate, putting the substrate into the solution, carrying out high-pressure solvothermal reaction together, taking out the solution after the reaction condition is 150 ℃ for 4 hours to obtain NH2-BDC modified TiO2A film. 18ml of DMF and 2ml of absolute methanol solution are mixed and 0.2172g of NH are added2BDC and 0.21ml tetra-n-butyl titanate, after complete dissolution, NH2-BDC modified TiO2Soaking the film in the solution, carrying out high-pressure solvothermal reaction under the pressure of 2MPa and under the reaction condition of 150 ℃ for 72h, and taking out to obtain TiO2@NH2-MIL-125(Ti)；
3. Then TiO2@NH2Connecting two ends of MIL-125(Ti) with a Gishy source meter by using a lead (a gold wire) to prepare a device for chemical resistance type gas-sensitive test;
4. placing the device in the device shown in FIG. 9, connecting a Giaxle lithium source meter, introducing dry air, aging for 12h under 5V voltage, and detecting the nitro explosive atmosphere with the detected visible light wavelength of 420-790 nm;
5. 2g of PA powder is filled into a U-shaped glass tube, dry air is introduced into two ends of the U-shaped glass tube, the U-shaped glass tube is heated for 24 hours at the temperature of 80 ℃, and adsorbed water vapor is discharged completely. Then the mixture is sealed and pre-enriched for 24 hours at room temperature to obtain PA steam with the concentration of 0.97 ppb.
6. And (3) introducing the steam in the step (5) into the device in the step (3), and monitoring the current change caused by introducing the PA by using a Giaxle source meter. The test results are shown in FIG. 10, with a response of 174% for 0.97ppb of PA.
Fig. 9 is a schematic diagram of an apparatus for testing an explosive with a chemiresistive sensor.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. MOX @ NH2-MOFs thin film material, characterized by NH2-MOFs are uniformly and continuously coated on MOX film, NH2The coating rate of the MOFs is 100%.
2. The thin film material of claim 1, wherein the MOX is a thin film with significant photocatalytic activity comprising nanoparticles, arrays of nanowires; for example, the MOX is TiO2Nanowires, ZnO and SnO2Preferably TiO2A nanowire.
3. The film material of claim 1, wherein the MOX material has a particle size of 50-300nm and a length of 1-4 μm.
4. The film material of claim 1, wherein said MOX @ NH2The MOFs film material is a uniform continuous coated core-sheath structure, NH2-MOFs with adjustable bandgap, said NH2-the band gap of the MOFs is 1.3-3.2 eV; the band gap of the MOX is 3.0-3.2 eV.
5. The MOX @ NH of any one of claims 1-42-a method for preparing a MOFs thin film material, characterized in that the method comprises the following steps:
a. preparing a MOX film on a non-conductive substrate;
b. packaging NH outside the MOX film in the step a by adopting a seed crystal assisted solvothermal method2-MOFs Material preparation MOX @ NH2-MOFs thin film materials.
6. The MOX @ NH of claim 52-MOFs thin film material preparation method, characterized in thatIn the step b, the temperature of the seed crystal assisted solvothermal method is 100-200 ℃, and the solvothermal time is 24-96h, preferably 72 h.
The packaging method in the step b comprises the following steps: adopting one of spin coating, dipping, pulling and in-situ growth methods to prepare NH2-the MOFs material is compounded on the MOX film; in-situ growth is preferred.
7. The MOX @ NH of claim 52-MOFs thin film material preparation method, characterized in that MOX is TiO2(ii) a Said TiO in step a2The preparation method of the film comprises the following steps: dissolving tetra-n-butyl titanate in a first solvent, soaking the substrate in the first solvent, and calcining to prepare the substrate with the seed crystal layer; then putting the substrate with the seed crystal layer into a polytetrafluoroethylene mold, adding tetra-n-butyl titanate and a second solvent, heating and calcining to prepare TiO2A film. Preferably, the first solvent is ethanol.
Preferably, the second solvent is a mixture of hydrochloric acid and water; the volume ratio of the hydrochloric acid to the water is 1: 1.
Preferably, the temperature of calcination is 430-460 ℃, preferably 450 ℃; the calcination time is 20-70 min.
Preferably, the preparation method of the amino-functionalized metal organic framework material comprises the following specific preparation steps: dissolving an organic ligand containing amino and metal salt in a mixed solvent of anhydrous methanol and DMF, uniformly mixing, heating for reaction, and drying to prepare the NH2-MOFs material.
8. The MOX @ NH of any one of claims 1-72Application of MOFs thin film material, characterized in that, the preparation method for preparing chemical resistance type sensor comprises the following steps:
at MOX @ NH2And fixedly connecting a conductive electrode on the MOFs thin film material, and connecting the conductive electrode with a power supply to prepare the chemical resistance type sensor.
9. The use of the chemiresistor sensor according to claim 8, for detecting the atmosphere of nitro explosives, wherein the specific detection method is as follows:
and applying voltage to the chemical resistance type sensor, placing the chemical resistance type sensor in the atmosphere of the nitro explosives, and detecting.
10. Use of a chemiresistive sensor according to claim 9, wherein the nitro-explosive is TNT, DNT, PA, RDX or a derivative thereof.
Preferably, the detection temperature is normal temperature.
Preferably, the wavelength of visible light is 420-790nm, which is detected under visible light.
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