CN113325036A - GO-MOF composite material and dimethylamine QCM sensor and preparation method thereof - Google Patents
GO-MOF composite material and dimethylamine QCM sensor and preparation method thereof Download PDFInfo
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- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 title claims abstract description 13
- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 17
- 239000013110 organic ligand Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 229910001994 rare earth metal nitrate Inorganic materials 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000007605 air drying Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000012621 metal-organic framework Substances 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000010453 quartz Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 9
- LGPVTNAJFDUWLF-UHFFFAOYSA-N 2-amino-4-fluorobenzoic acid Chemical compound NC1=CC(F)=CC=C1C(O)=O LGPVTNAJFDUWLF-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- -1 11-mercapto-1-undecanol ethanol Chemical compound 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- MMWFMFZFCKADEL-UHFFFAOYSA-N 2-fluoro-4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1F MMWFMFZFCKADEL-UHFFFAOYSA-N 0.000 claims description 5
- NSTREUWFTAOOKS-UHFFFAOYSA-N 2-fluorobenzoic acid Chemical group OC(=O)C1=CC=CC=C1F NSTREUWFTAOOKS-UHFFFAOYSA-N 0.000 claims description 5
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 239000010413 mother solution Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 239000013081 microcrystal Substances 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 10
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims 1
- 238000002203 pretreatment Methods 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 12
- 230000004044 response Effects 0.000 abstract description 10
- 230000035945 sensitivity Effects 0.000 abstract description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 56
- 238000003380 quartz crystal microbalance Methods 0.000 description 39
- 239000002131 composite material Substances 0.000 description 21
- 239000007789 gas Substances 0.000 description 18
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000282465 Canis Species 0.000 description 1
- 239000013148 Cu-BTC MOF Substances 0.000 description 1
- 239000013177 MIL-101 Substances 0.000 description 1
- 239000013132 MOF-5 Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910003101 Y(NO3)3·6H2O Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000000622 irritating effect Effects 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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Abstract
The invention belongs to the technical field of dimethylamine gas detection, and particularly relates to a GO-MOF composite material, a dimethylamine QCM sensor and a preparation method thereof. The invention aims to solve the problem that the conventional dimethylamine sensor has low sensitivity. The technical scheme of the invention is a preparation method of a GO-MOF composite material, which comprises the following steps: organic ligand, rare earth metal nitrate, auxiliary connecting agent, DMF, H2Mixing O, nitric acid and graphene oxide, and uniformly dispersing; reacting for 24-72 h at 105-130 ℃; cooling, filtering and air drying; washing with anhydrous DMF, and replacing DMF solvent in the gap with ethanol; and (5) drying in vacuum. And further preparing the dimethylamine QCM sensor based on the GO-MOF composite sensitive film on the basis. The invention adopts GO-MOF composite material as sensitive film and QCM as conversion device to construct a high-efficiency sensor for dimethylamine gas, and has the advantages of quick response, good selectivity, high sensitivity and the likeAnd (4) point.
Description
Technical Field
The invention belongs to the technical field of dimethylamine gas detection, and particularly relates to a GO-MOF composite material, a dimethylamine QCM sensor and a preparation method thereof.
Background
Dimethylamine (DMA) is a widely used drug,Dyes, insecticides, rubber vulcanization accelerators, rocket propellants and the like, which have ammonia-like odors at high concentrations and gases with fish-rot malodor (boiling point 7 ℃) at low concentrations, have strong irritating effects on human skin, eyes and respiratory tract, and cause great harm to human bodies due to excessive exposure or inhalation. Dimethylamine gas is determined as a typical environmental gas pollutant in various chemical production (GB4554-93), and the maximum allowable emission concentration is 5mg/m3. At present, dimethylamine detection and analysis methods mainly comprise a chromatography detection method, a mass spectrum direct detection method, a spectrum analysis method, a canine olfactory system and a sensor detection method, but the methods have the defects of complex operation, long time consumption, analysis and detection hysteresis, complex sample pretreatment and detection procedures and the like. Due to the lack of a suitable sensitive membrane which can respond to dimethylamine with high sensitivity and high selectivity, the currently adopted sensing monitoring method for the efficient detection of dimethylamine has not been reported at present.
Relevant researches show that the conventional dimethylamine sensor is a semiconductor sensing device based on a nano sensitive film, and has the problems of low detection sensitivity, high working temperature, cross sensitivity and the like. Metal-Organic Frameworks (MOFs) are crystalline porous materials with periodic network structures, have the advantages of high porosity, large specific surface area, adjustable pore diameter and the like, and have wide application prospects in the field of gas sensing. Research has shown that MOFs have good affinity and adsorption capacity for various VOCs, such as HKUST-1, MOF-5, MIL-101, ZIF-8, etc. However, the selectivity of the MOFs material is poor, so that the application of the MOFs material in sensing detection is greatly limited.
Disclosure of Invention
The invention aims to solve the problem that the conventional dimethylamine sensor has low sensitivity.
The technical scheme of the invention is a preparation method of a graphene oxide-metal organic framework (GO-MOF) composite material, which comprises the following steps:
step (1), organic ligand, rare earth metal nitrate, auxiliary connecting agent, DMF, H2Mixing O, nitric acid and graphene oxide, and uniformly dispersing to obtain a synthetic mother solution;
reacting for 24-72 h at 105-130 ℃; cooling, filtering and air drying; washing with anhydrous DMF, and replacing DMF solvent in the gap with ethanol; and (5) drying in vacuum.
Furthermore, the addition amount of the graphene oxide is 1-20% of the mass of the rare earth metal nitrate, the rare earth metal nitrate is 1-3 times of the molar amount of the organic ligand, and the auxiliary connecting agent is 5-20 times of the molar amount of the organic ligand.
Specifically, the organic ligand is 1, 4-naphthalene dicarboxylic acid.
Wherein the rare earth metal is Eu, Y or Tb.
Further, the auxiliary connecting agent is 2-fluorobenzoic acid, 2-fluoro-4-nitrobenzoic acid or 2-amino-4-fluorobenzoic acid.
Wherein the vacuum drying is vacuum drying at 150 ℃ for 12 h.
The invention also provides the GO-MOF composite material prepared by the method.
The invention further provides a preparation method of the dimethylamine QCM sensor based on the GO-MOF composite sensitive film, which comprises the following steps:
(1) organic ligand, rare earth metal nitrate, auxiliary connecting agent, N-Dimethylformamide (DMF), and H2Mixing O, nitric acid and graphene oxide, and uniformly dispersing to obtain a synthetic mother solution;
(2) pretreating a quartz microcrystal Tianping gold electrode, modifying a hydroxyl monomolecular layer, covering the back of a QCM (quartz crystal microbalance) by PDMS (polydimethylsiloxane), placing the QCM into a synthetic mother solution of GO-MOF, reacting at 115 ℃ for 24 hours, cooling to room temperature, replacing DMF (dimethyl formamide) in gaps of the MOF by ethanol, and drying in vacuum.
Further, in the step (1), the addition amount of the graphene oxide is 1-20% of the mass of the rare earth metal nitrate, the rare earth metal nitrate is 1-3 times of the molar weight of the organic ligand, and the auxiliary connecting agent is 5-20 times of the molar weight of the organic ligand.
Specifically, in the step (1), the organic ligand is 1, 4-naphthalene dicarboxylic acid.
Wherein, in the step (1), the rare earth metal is Eu, Y or Tb.
Further, in the step (1), the auxiliary linking agent is 2-fluorobenzoic acid, 2-fluoro-4-nitrobenzoic acid or 2-amino-4-fluorobenzoic acid.
Wherein, in the step (1), the vacuum drying is carried out for 12 hours at 150 ℃.
Specifically, in the step (2), the QCM quartz vibrating plate is an AT cut quartz crystal, and the fundamental frequency is 5-9 MHz.
Preferably, in the step (2), the QCM quartz vibrating piece has a diameter of 1.2cm, and comprises two electrodes respectively distributed on the front and back sides of the quartz piece; the front side of the electrode comprises a circular electrode with the diameter of 1.0cm, and the back side of the electrode comprises two circular arc electrodes and a circular electrode, wherein one circular arc electrode is connected with the circular electrode; the radian of the two arc electrodes is 2 pi/5, and the width is 1.0 mm; the diameter of the circular electrode is 0.5 cm; the electrode material is gold, and the fundamental frequency is 9 MHz.
In the step (2), the pretreatment is to soak the QCM respectively in acetone, ethanol and deionized water for 10min, and then blow-dry the QCM with nitrogen for later use.
Further, in the step (2), the modification of the hydroxyl monomolecular layer is to put the QCM into an 11-mercapto-1-undecanol ethanol solution for reaction for 2 hours, wash the redundant solution with ethanol, and blow-dry with nitrogen for later use.
Specifically, in the step (2), the vacuum drying is carried out at 165 ℃ for 2 h.
The invention also provides the dimethylamine QCM sensor prepared by the method.
The MOF central metal ions used include Eu3+、Y3+、Tb3+The rare earth elements are mixed, o-fluorobenzoic acid, 2-fluoro-4-nitrobenzoic acid or 2-amino-4-fluorobenzoic acid is used as an auxiliary connecting agent, 1, 4-naphthalenedicarboxylic acid is used as an organic ligand to form the porous material with the face cubic crystal structure of octahedral cage structure and tetrahedral structure, and different cage structures are mutually penetrated and connected to form about
Can only pass through small molecule triangular structures.
Graphene oxide with rich oxygen-containing groups on the surface is added in the synthesis process of the MOF, so that the MOF can form new gaps with the graphene oxide while the original gaps are reserved. The graphene oxide has good chemical stability, can participate in the synthesis of the MOF to coordinate with central metal ions to form more gaps, and can also be used as an effective dispersion and attachment material to provide a large specific surface area for the MOF surface to synergistically enhance the adsorption of amine gases.
The MOF material based on the rare earth metal ions has stronger electron-withdrawing capability (metal ions, -F, -C)6H5Etc.) has strong affinity to amine substances with strong electron donating ability, and the triangular gaps on the MOF surface are only
Can preferentially adsorb small molecule gas. The difference in molecular size between dimethylamine and trimethylamine (as calculated by Chembio 3D software, dimethylamine has a molecular diameter of about
The molecular diameter of trimethylamine is about
) Can adsorb dimethylamine with high selectivity. Because the size of the trimethylamine molecule is smaller than the approximate pore size, there is also some adsorption, but much smaller than the adsorption amount of dimethylamine. In addition, for nonpolar molecules N2、O2、CO2And the adsorption capacity is poor, so that the method can be suitable for the conventional gas environment. While the large molecules such as ethyl acetate, benzene, toluene, chloroform, etc. commonly found in VOCs cannot pass through the MOF voids, most of the small molecules have poor polar adsorption capacity.
By optimizing the reaction temperature, time, the types of central metal ions and ligands, the composition molar ratio and the like, the central metal ions of the MOF material are Eu3+、Y3+、Tb3+Providing nitrate of rare earth ions, wherein the ligand is naphthalenedicarboxylic acid, and the auxiliary connecting agent is o-fluorodicarboxylic acid and 2-fluoro-4-nitroBenzoic acid or 2-amino-4-fluorobenzoic acid, wherein the addition amount of graphene oxide is 1-20% of the mass of the rare earth metal salt, the reaction temperature is 105-130 ℃, and the reaction time is 24-72 hours. Under the optimized condition, the triangular gap range of the MOF surface can be prepared (obtained by theoretical calculation of a ball stick model)
Dimethylamine gas molecules can be preferentially adsorbed.
The constructed dimethylamine sensor comprises: and (3) forming a QCM film by using the QCM basic device, QCM surface modification and GO-MOF composite material.
The structure of the present invention using QCM is shown in fig. 1. The quartz vibrating plate has a diameter of 1.2cm, and comprises two electrodes respectively distributed on the front and back sides of the quartz plate. The front side of the electrode comprises a circular electrode with the diameter of 1.0cm, and the back side of the electrode comprises two circular arc electrodes and a circular electrode, wherein one circular arc electrode is connected with the circular electrode. The radian of the two arc electrodes is 2 pi/5, and the width is 1.0 mm; the diameter of the circular electrode is 0.5 cm; the electrode material is gold, and the fundamental frequency is 9 MHz.
The GO-MOF composite material self-assembles on the surface of the QCM. 1) On the selected QCM surface, monolayer modification of hydroxyl groups is first performed, allowing the MOF material to grow a layer of MOF particles on the QCM surface. The method comprises the following specific steps: and soaking the QCM in acetone, ethanol and deionized water respectively, ultrasonically washing, and drying by nitrogen for later use. And (3) putting the cleaned QCM into an 11-mercapto-1-undecanol ethanol solution with a certain concentration for reaction for a certain time, modifying the surface with-OH, flushing the redundant solution with ethanol, and drying with nitrogen for later use. 2) Covering the back of the modified QCM sheet with PDMS to prevent the back electrode from being covered and polluted by MOF, then putting the QCM sheet into MOF synthesis mother liquor, carrying out hydrothermal reaction for a certain time at a certain temperature, cooling to room temperature, taking out, soaking with methanol or ethanol for a certain time to replace DMF solvent in MOF gaps, taking out, vacuum drying and connecting with a working electrode to obtain the dimethylamine sensor.
The invention discloses a Graphene Oxide (GO) modified MOF composite sensitive membrane with good selectivity to amine components by utilizing the characteristics of void screening and easy functionalized modification of a composite MOF material, wherein the amine molecules are nitrogen-containing organic matters with strong alkalinity, and the differences of the polarity and alkalinity of the amine molecules and common VOCs are large. And the related functionalized composite sensitive film is organically combined with QCM to construct a dimethylamine sensing device with quick response and good selectivity.
The invention has the beneficial effects that:
according to the invention, the GO-MOF composite material is used as a sensitive film, and the QCM is used as a conversion device to construct a high-efficiency sensor for the dimethylamine gas, and the sensor has the advantages of fast response, good selectivity, high sensitivity and the like.
Drawings
FIG. 1, a schematic view of QCM structure and surface modification; the left figure is a structural schematic diagram of the QCM quartz vibrating plate, wherein 1, 2 and 3 are shown as quartz, and 4 is shown as a metal electrode; the right figure is a schematic diagram of the process of growing the composite material on the surface of the QCM.
FIG. 2 is a scanning electron microscope morphology characterization diagram of Eu-MOF (a), GO-MOF (b, c).
FIG. 3, schematic representation of GO-MOF @ QCM sensor detecting dimethylamine; the left side is the frequency meter, and the right side is QCM sensor and test box.
FIG. 4, GO-MOF @ QCM sensor is sensitive to 10ppm of dimethylamine gas, with frequency change on the ordinate and time on the abscissa.
Fig. 5, response of the sensor at different dimethylamine concentrations, frequency change on the ordinate and gas concentration on the abscissa.
FIG. 6, Selectivity of sensor
Detailed Description
Example 1 preparation of GO-MOF composites
1, 4-naphthalenedicarboxylic acid (0.0331mmol), Eu (NO)3)3·5H2O (0.0405mmol), 2-fluorobenzoic acid (0.348mmol) and graphene oxide (10% of europium nitrate) are added respectivelyAdding a certain amount of DMF, H2O and HNO3The mixed solution is evenly mixed and ultrasonically treated for 10min, the mixture is evenly dispersed and then put into a reaction kettle to be sealed and heated to 120 ℃ for reaction for 24h, and the mixture is cooled to room temperature. Washed, filtered and air dried. Washing the synthesized Eu-MOF sample with 10mL of anhydrous DMF, soaking in 10mL of ethanol for 3 days, replacing the ethanol for 3 times every day, replacing DMF solvent in gaps, and then drying the solid in vacuum at 150 ℃ for 12 hours to obtain the activated sample GO-MOF composite material.
Example 2 preparation of GO-MOF composites
1, 4-naphthalenedicarboxylic acid (0.0415mmol), Y (NO)3)3·6H2O (0.0584mmol), 2-amino-4-fluorobenzoic acid (0.305mmol) and graphene oxide (5% of europium nitrate) are respectively added into a certain amount of DMF and H2O and HNO3The mixed solution is evenly mixed and ultrasonically treated for 10min, the mixture is evenly dispersed and then put into a reaction kettle to be sealed and heated to 105 ℃ for reaction for 36h, and the mixture is cooled to room temperature. Washed, filtered and air dried. Washing the synthesized Eu-MOF sample with 10mL of anhydrous DMF, soaking in 10mL of ethanol for 3 days, replacing the ethanol for 3 times per day, replacing DMF solvent in the net structure, and then drying the solid in vacuum at 150 ℃ for 12 hours to obtain the activated sample GO-MOF composite material.
Example 3 preparation of GO-MOF composites
1, 4-naphthalenedicarboxylic acid (0.0415mmol), Y (NO)3)3·6H2O (0.0415mmol), 2-amino-4-fluorobenzoic acid (0.2075mmol) and graphene oxide (the mass is 1% of that of europium nitrate) are respectively added into a certain amount of DMF and H2O and HNO3The mixed solution is evenly mixed and ultrasonically treated for 10min, the mixture is evenly dispersed and then put into a reaction kettle to be sealed and heated to 110 ℃ for reaction for 40h, and the mixture is cooled to room temperature. Washed, filtered and air dried. Washing the synthesized Eu-MOF sample with 10mL of anhydrous DMF, soaking in 10mL of ethanol for 3 days, replacing the ethanol for 3 times per day, replacing DMF solvent in the net structure, and then drying the solid in vacuum at 150 ℃ for 12 hours to obtain the activated sample GO-MOF composite material.
Example 4 preparation of GO-MOF composites
1, 4-naphthalenedicarboxylic acid (0.0415mmol)，Y(NO3)3·6H2O (0.1245mmol), 2-amino-4-fluorobenzoic acid (0.8300mmol) and graphene oxide (the mass is 20% of that of europium nitrate) are respectively added into a certain amount of DMF and H2O and HNO3The mixed solution is evenly mixed and ultrasonically treated for 10min, the mixture is evenly dispersed and then put into a reaction kettle to be sealed and heated to 130 ℃ for reaction for 72h, and the mixture is cooled to room temperature. Washed, filtered and air dried. Washing the synthesized Eu-MOF sample with 10mL of anhydrous DMF, soaking in 10mL of ethanol for 3 days, replacing the ethanol for 3 times per day, replacing DMF solvent in the net structure, and then drying the solid in vacuum at 150 ℃ for 12 hours to obtain the activated sample GO-MOF composite material.
Example 5 preparation of dimethylamine QCM sensor based on GO-MOF composite sensitive film
The structure using QCM is shown in fig. 1. The quartz vibrating plate has a diameter of 1.2cm, and comprises two electrodes respectively distributed on the front and back sides of the quartz plate. The front side of the electrode comprises a circular electrode with the diameter of 1.0cm, and the back side of the electrode comprises two circular arc electrodes and a circular electrode, wherein one circular arc electrode is connected with the circular electrode. The radian of the two arc electrodes is 2 pi/5, and the width is 1.0 mm; the diameter of the circular electrode is 0.5 cm; the electrode material is gold, and the fundamental frequency is 9 MHz.
And soaking the QCM in acetone, ethanol and deionized water respectively for 10min, and then blowing the QCM to dry by nitrogen for later use. And (3) putting the cleaned QCM into 5 mu M11-mercapto-1-undecanol ethanol solution for reaction for 2h, modifying the surface with-OH, washing the redundant solution with ethanol, and drying with nitrogen for later use. Covering the back of the modified QCM sheet with PDMS to prevent the back electrode from being covered and polluted by MOF, then putting the QCM sheet into the synthetic mother liquor in the embodiment 1, carrying out hydrothermal reaction at 115 ℃ for 24h, cooling to room temperature, taking out, soaking in ethanol for 24h to replace DMF solvent in MOF gaps, taking out, and carrying out vacuum drying at 165 ℃ for 2 h. And obtaining the dimethylamine QCM sensor based on the GO-MOF composite sensitive film.
Example 6 response test of dimethylamine sensor
The experiment adopts the experimental device of FIG. 3 to carry out the test of GO-MOF @ QCM dimethylamine sensor.
The specific test process is as follows: in the experiment, the QCM oscillating circuit is supplied by a 9V battery, a KEYSIGHT frequency meter (0-350 MHz) is adopted to collect the QCM frequency, and the test sensitivity is 0.1 Hz. Before each test, the interference gas in the box is replaced by 3 times of vacuum-nitrogen circulation, nitrogen is used as auxiliary gas, and a certain amount of dimethylamine gas is injected by a gas chromatography injector after the frequency is stable. The gas box volume was 17.7L and the dimethylamine concentration was controlled by the volume of dimethylamine injected. As shown in fig. 4, the method has excellent response speed (response time < 30s) and recovery capability (120s) for dimethylamine detection; as shown in FIG. 5, the sensor has good linearity in the dimethylamine concentration range of 1-100 ppm, and the sensitivity is 12 Hz/ppm.
The frequency response of the sensor to trimethylamine, ammonia, chloroform, toluene and formaldehyde gas under the same concentration is tested according to the same steps, as shown in fig. 6, the sensor has the highest response to dimethylamine, the change of 20ppm is 140Hz, which is 3.5 times of the change of trimethylamine, and the sensor has almost no response to other organic gases.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A preparation method of a GO-MOF composite material is characterized by comprising the following steps:
step (1), organic ligand, rare earth metal nitrate, auxiliary connecting agent, dimethyl sulfoxide (DMF), and H2Mixing O, nitric acid and graphene oxide, and uniformly dispersing to obtain a synthetic mother solution;
reacting for 24-72 h at 105-130 ℃; cooling, filtering and air drying; washing with anhydrous DMF, and replacing DMF solvent in the gap with ethanol; and (5) drying in vacuum.
2. The preparation method of claim 1, wherein the addition amount of the graphene oxide is 1-20% of the mass of the rare earth metal nitrate, the rare earth metal nitrate is 1-3 times of the molar amount of the organic ligand, and the auxiliary linking agent is 5-20 times of the molar amount of the organic ligand.
3. The method of claim 1, wherein the organic ligand is 1, 4-naphthalene dicarboxylic acid; preferably, the rare earth metal is Eu, Y or Tb; preferably, the auxiliary linking agent is 2-fluorobenzoic acid, 2-fluoro-4-nitrobenzoic acid or 2-amino-4-fluorobenzoic acid.
4. The method of claim 1, wherein the vacuum drying is vacuum drying at 150 ℃ for 12 hours.
5. A GO-MOF composite material prepared by the method of any one of claims 1 to 4.
6. A preparation method of a dimethylamine QCM sensor based on a GO-MOF composite sensitive film, which is characterized by comprising the step (1) in the method of any one of claims 1 to 4, and further comprising the following steps: hydroxyl monolayer modification is carried out on the surface of a gold electrode of a quartz microcrystal balance QCM, the back of the QCM is covered by a PDMS film, the QCM is placed in GO-MOF synthesis mother liquor, the reaction is carried out for 24-72 h at 105-130 ℃, then the QCM is cooled to room temperature, DMF in MOF gaps is replaced by ethanol, and vacuum drying is carried out.
7. The preparation method according to claim 6, wherein the QCM quartz vibrating plate is an AT cut quartz crystal with a fundamental frequency of 5-9 MHz; preferably, the QCM quartz vibrating piece has the diameter of 1.2cm, comprises two electrodes and is respectively distributed on the front side and the back side of the quartz piece; the front side of the electrode comprises a circular electrode with the diameter of 1.0cm, and the back side of the electrode comprises two circular arc electrodes and a circular electrode, wherein one circular arc electrode is connected with the circular electrode; the radian of the two arc electrodes is 2 pi/5, and the width is 1.0 mm; the diameter of the circular electrode is 0.5 cm; the electrode material is gold, and the fundamental frequency is 9 MHz.
8. The preparation method of claim 6, wherein the pre-treatment comprises soaking the QCM in acetone, ethanol, deionized water for 10min, respectively, and then blowing the QCM with nitrogen for standby; preferably, the modification of the hydroxyl monomolecular layer is to put the QCM into an 11-mercapto-1-undecanol ethanol solution for reaction for 2 hours, wash the redundant solution with ethanol, and blow-dry with nitrogen for later use.
9. The method of claim 6, wherein the vacuum drying is carried out at 165 ℃ for 2 hours.
10. Dimethylamine QCM sensor prepared according to the method of any of claims 6 to 9.
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