CN110759351B - Crystal oscillator surface molecular sieve membrane material and preparation method and application thereof - Google Patents
Crystal oscillator surface molecular sieve membrane material and preparation method and application thereof Download PDFInfo
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- CN110759351B CN110759351B CN201810832274.5A CN201810832274A CN110759351B CN 110759351 B CN110759351 B CN 110759351B CN 201810832274 A CN201810832274 A CN 201810832274A CN 110759351 B CN110759351 B CN 110759351B
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 175
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 175
- 239000013078 crystal Substances 0.000 title claims abstract description 102
- 239000012528 membrane Substances 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 56
- 238000000576 coating method Methods 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001308 synthesis method Methods 0.000 claims abstract description 6
- 239000011268 mixed slurry Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims description 30
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 26
- 229910052737 gold Inorganic materials 0.000 claims description 26
- 239000010931 gold Substances 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000010453 quartz Substances 0.000 claims description 22
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 239000012808 vapor phase Substances 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 6
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 4
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- 229910002113 barium titanate Inorganic materials 0.000 claims description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 238000002715 modification method Methods 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 238000010335 hydrothermal treatment Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 230000005685 electric field effect Effects 0.000 claims 1
- 239000000523 sample Substances 0.000 abstract description 14
- 238000001035 drying Methods 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 9
- 238000011065 in-situ storage Methods 0.000 abstract description 7
- 229910001872 inorganic gas Inorganic materials 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 13
- 229910021536 Zeolite Inorganic materials 0.000 description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 9
- 239000010457 zeolite Substances 0.000 description 9
- 239000012690 zeolite precursor Substances 0.000 description 8
- 238000001514 detection method Methods 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- 230000010355 oscillation Effects 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/205—Faujasite type, e.g. type X or Y using at least one organic template directing agent; Hexagonal faujasite; Intergrowth products of cubic and hexagonal faujasite
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
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Abstract
The invention belongs to the field of sensor probe materials, and particularly relates to a crystal oscillator surface molecular sieve membrane material and a preparation method and application thereof. Preparing a molecular sieve membrane at a specific position on the surface of a crystal oscillator, firstly preparing a molecular sieve precursor sol, and coating the molecular sieve precursor sol or the mixed slurry of the molecular sieve precursor sol and nano molecular sieve powder at the specific position on the surface of the crystal oscillator by adopting a rotary coating method. After low-temperature drying treatment, the crystal oscillator coated with the molecular sieve precursor is placed in a reaction kettle, and the molecular sieve precursor is promoted to crystallize by utilizing the steam pressure generated by water. The method combines the advantages of a coating method and an in-situ synthesis method, can prepare the molecular sieve membrane with high interface bonding strength at a specific position on the surface of the crystal oscillator, and the thickness of the molecular sieve membrane and the type of the molecular sieve can be regulated and controlled. The crystal oscillator loaded with the molecular sieve membrane has good signal corresponding performance and can be used for detecting various organic and inorganic gases.
Description
Technical Field
The invention belongs to the field of sensor probe materials, and particularly relates to a crystal oscillator surface molecular sieve membrane material, and a preparation method and application thereof.
Background
With the increasing living standard of people, the environmental pollution problem caused by economic development is increasingly serious. Volatile gas in the air seriously affects the health of people, and organic gas in the air is also the main reason for haze formation. The molecular sieve has specific selectivity to organic gas, and can realize good sensitivity to low-concentration gas through the structural design and modification of molecular sieve pore paths.
The project aims to adopt a piezoelectric ceramic resonant sensor such as quartz or zirconia as a detection sensor, a molecular adsorption film is plated on the detection sensor for adsorbing gas molecules deposited on the detection sensor, the whole mass of the sensor is increased due to the adsorption of the gas, so that the frequency is correspondingly linearly changed, the mass of the gas deposited on the surface of the sensor can be obtained by testing the frequency difference before and after adsorption, and the crystal oscillator realizes detection through the piezoelectric effect of crystals.
The core part of the resonant sensor is a crystal oscillator formed by two circular electrodes on the surface of the crystal oscillator and an oscillation formed by a feedback and energy supply circuit. And the oscillation frequency of the quartz crystal is influenced by the contamination amount of the surface deposition particles, and the larger the contamination amount is, the smaller the oscillation frequency of the crystal is, so that the contamination amount of the surface particles can be measured. As shown in fig. 3 (a) -3 (b), the quartz crystal 1 is coated with metal material (gold or aluminum) on both sides as electrodes 2, driven by a resonant circuit, and a time-dependent electric field 3 is formed between the electrodes to oscillate the quartz crystal 1 at a frequency determined by the total mass of the quartz crystal 1 itself and the substances attached to the outer surfaces of the electrodes 2. When gas molecules adsorbed by the gas sensitive membrane accumulate (mass increases) on the electrodes, all of the adsorbed gas will shift as the crystal oscillates. Thus, as the frequency of crystal movement is reduced by the increase in mass, changes in the quality of the deposit are detected by monitoring changes in the crystal frequency.
In order to obtain the optimal sensitivity of the crystal oscillator, a molecular sieve membrane with uniform load and firm combination needs to be prepared on the surface of the quartz crystal oscillator gold electrode. At present, the preparation method of the molecular sieve membrane mainly comprises a coating method and an in-situ synthesis method. The coating method is to coat slurry consisting of the molecular sieve and the binder on the surface of the carrier and load the molecular sieve on the surface of the matrix through physical bonding force. The method has the advantages that the synthesis of the molecular sieve is separated from the coating step, the crystal size and the coating thickness of the molecular sieve coating are easy to control, and the method has the defect that the bonding force between the coating and the substrate is weak. Another synthesis method is in-situ hydrothermal synthesis, which comprises the steps of immersing a substrate into a molecular sieve mother solution, and growing molecular sieve crystals on the surface of the substrate in situ under the conditions of high temperature and high pressure. The method can prepare the molecular sieve coating with uniform load and firm combination on the quartz substrate. However, since the quartz substrate needs to be immersed in the molecular sieve mother solution in the process of growing the molecular sieve in situ, the growth of molecular sieve crystals on other parts of the substrate except the gold electrode cannot be avoided.
Disclosure of Invention
The invention aims to provide a crystal oscillator surface molecular sieve membrane material and a preparation method and application thereof.
The technical scheme of the invention is as follows:
the molecular sieve film material for crystal oscillator surface has gold electrodes plated on two sides of crystal oscillator substrate, and has molecular sieve film of thickness below 1 micron and interface binding force greater than 3MPa.
The crystal oscillator surface molecular sieve membrane material is characterized in that the crystal oscillator substrate is a piezoelectric ceramic substrate: quartz, silicon, zirconia, or barium titanate.
The molecular sieve of the crystal oscillator surface molecular sieve membrane material adopts a ZSM-5 type molecular sieve, a beta type molecular sieve, a Y type molecular sieve, an SSZ-13 type molecular sieve, an A type molecular sieve or the molecular sieve subjected to modification treatment, and the modification method of the molecular sieve is noble metal loading modification, alkali metal modification or alkaline earth metal modification.
The molecular sieve membrane material on the surface of the crystal oscillator has the thickness of 50-1000 nanometers.
Firstly, coating colloidal molecular sieve precursor or mixed slurry of the colloidal molecular sieve precursor and nano molecular sieve powder on the surface of a gold electrode of a crystal oscillator substrate in a rotating manner and carrying out heat treatment; then, converting the molecular sieve precursor into a molecular sieve crystal through vapor phase treatment, and realizing firm combination between the coating and the carrier; the colloidal molecular sieve precursor comprises a molecular sieve synthesis basic unit or consists of molecular sieve colloidal particles which are not completely crystallized, the crystal size of the molecular sieve is controlled by changing the composition, the synthesis temperature and the synthesis time of the colloidal molecular sieve precursor, and the film thickness is controlled by controlling the spin coating condition; after the colloidal molecular sieve precursor is coated on the surface of a gold electrode of a crystal oscillator substrate, the heat treatment temperature is 40-80 ℃, and the thickness of a molecular sieve film is controlled by controlling the steam phase composition, the reaction temperature and the reaction time.
The preparation method of the crystal oscillator surface molecular sieve membrane material comprises the following steps of:
(1) Mixing a silicon source, an aluminum source, a template agent and deionized water in proportion, wherein the molar ratio of the silicon source to the aluminum source to the template agent to the deionized water is 1:0.001 to 0.2:0 to 1.0 (the template is generally 0.1 to 1.0): 5 to 200;
(2) Hydrothermal treatment: after the silicon source is completely hydrolyzed, aging the solution at 40 +/-5 ℃ for 24-96 hours to form a colloidal molecular sieve precursor;
(3) Adjusting the colloid concentration: adding an organic solvent into the colloidal molecular sieve precursor: ethanol, methanol, isopropanol or tween, and the colloidal molecular sieve precursor is diluted to the concentration of 5-50 wt%.
In the preparation method of the crystal oscillator surface molecular sieve membrane material, in the preparation process of the colloidal molecular sieve precursor, a silicon source is one or more than two of tetraethoxysilane, silica sol or white carbon black, and an aluminum source is one or more than two of sodium metaaluminate, aluminum nitrate, aluminum sulfate, aluminum isopropoxide or aluminum foil; when preparing a colloidal ZSM-5 molecular sieve precursor, adopting tetrapropyl ammonium hydroxide, tetrapropyl ammonium bromide or a mixture of the tetrapropyl ammonium hydroxide and the tetrapropyl ammonium bromide as a template agent; when the colloidal state beta molecular sieve precursor is prepared, tetraethyl ammonium hydroxide, tetraethyl ammonium bromide or a mixture of tetraethyl ammonium hydroxide and tetraethyl ammonium bromide is used as a template agent; when preparing the colloidal Y-type molecular sieve precursor, tetramethyl ammonium hydroxide, tetramethyl ammonium bromide or a mixture of the tetramethyl ammonium hydroxide and the tetramethyl ammonium bromide is used as a template agent.
The preparation method of the crystal oscillator surface molecular sieve membrane material is characterized in that the nano molecular sieve membrane material is prepared on the surface of a gold electrode of a crystal oscillator substrate, the used steam phase is pure water or tetrapropyl ammonium hydroxide aqueous solution or ethylenediamine and triethylamine aqueous solution, the reaction temperature is 100-250 ℃, and the reaction time is 3-200 hours.
The application of the crystal oscillator surface molecular sieve membrane material realizes the adsorption of characteristic gas by utilizing the pore structure, hydrophilic and hydrophobic properties and the internal electric field action of a specific type of molecular sieve, and the adsorption quantity is determined by the change of the crystal oscillator frequency.
The design idea of the invention is as follows:
in order to adapt to the development of a high-sensitivity quartz crystal oscillator microbalance technology, the invention provides a preparation method of a molecular sieve membrane on the surface of a crystal oscillator, which combines a coating method and an in-situ synthesis method at a specific position on the surface of the crystal oscillator to prepare the molecular sieve membrane with uniform load, firm combination and controllable load and coating thickness.
The beneficial effects and specific innovation points of the invention are as follows:
(1) The molecular sieve membrane can be prepared at a specific position on the surface of a crystal oscillator.
(2) The interface bonding force between the molecular sieve membrane and the substrate is more than 3MPa.
(3) The thickness of the molecular sieve membrane is between 50 nanometers and 1 micron, and the molecular sieve crystal is a nanometer or submicron molecular sieve crystal.
(4) The quartz crystal oscillator molecular sieve probe has good sensitivity and precision of more than 10 -8 g/cm 2 。
In a word, the invention prepares the molecular sieve membrane at the specific position of the crystal oscillator surface, firstly prepares the precursor sol of the molecular sieve, and adopts the rotary coating method to coat the precursor sol of the molecular sieve or the mixed slurry of the precursor sol of the molecular sieve and the nano molecular sieve powder at the specific position of the crystal oscillator surface. After low-temperature drying treatment, the crystal oscillator coated with the molecular sieve precursor is placed in a reaction kettle, and the molecular sieve precursor is promoted to crystallize by utilizing the steam pressure generated by water. The method combines the advantages of a coating method and an in-situ synthesis method, can prepare the molecular sieve membrane with high interface bonding strength at a specific position on the surface of the crystal oscillator, and the thickness of the molecular sieve membrane can be regulated and controlled with the type of the molecular sieve. The crystal oscillator loaded with the molecular sieve membrane has good signal corresponding performance and can be used for detecting various organic and inorganic gases.
Drawings
FIG. 1 is a flow chart of controllable preparation of a binderless molecular sieve membrane by coating a molecular sieve precursor and combining with vapor phase inversion.
Fig. 2 (a) -2 (b) are the morphologies of the molecular sieve membrane on the surface of the crystal oscillator. Wherein, fig. 2 (a) is a macro topography, and fig. 2 (b) is a partial enlarged view.
FIGS. 3 (a) -3 (b) are schematic diagrams of the electric field and oscillation frequency of the 15MHz piezoelectric quartz crystal. Fig. 3 (a) is a perspective view, and fig. 3 (b) is a front view. In the figure, the reference number 1 is a quartz crystal; 2, an electrode; 3 electric field.
Detailed Description
In the specific implementation process, the molecular sieve precursor sol is firstly dripped on a gold electrode of a crystal oscillator substrate, and the precursor sol is uniformly coated on the gold electrode through a rotary coating machine. And then, the substrate coated with the precursor sol in a positioning mode is placed above a reaction kettle filled with a small amount of deionized water, the molecular sieve precursor is promoted to be converted into molecular sieve crystals through steam, and finally the template agent in the molecular sieve film is removed through an atmosphere sintering furnace. Wherein, the molecular sieve membrane only exists on the surface of the gold electrode, the thickness of the molecular sieve membrane is less than 1 micron, and the interface bonding force between the molecular sieve membrane and the gold electrode is more than 3MPa. The crystal oscillator substrate is made of quartz, silicon, or zirconium oxide, barium titanate and other ceramic substrates. The molecular sieve comprises ZSM-5 type molecular sieve, beta type molecular sieve, Y type molecular sieve, SSZ-13 type molecular sieve, A type molecular sieve or the molecular sieve after modification treatment. The molecular sieve modification method comprises the steps of loading noble metal and residual alkali metal or alkaline earth metal.
As shown in FIG. 1, the preparation method of the crystal oscillator surface nano molecular sieve membrane comprises cleaning → coating → vapor phase inversion → baking. Firstly, coating colloidal molecular sieve precursor or mixed slurry of the colloidal molecular sieve precursor and nano molecular sieve powder on a substrate surface electrode or a specific position on the surface of a crystal oscillator substrate in a rotating manner, and carrying out heat treatment; then, converting the molecular sieve precursor into a molecular sieve crystal through vapor phase treatment, and realizing firm combination between the coating and the carrier; the colloidal molecular sieve precursor comprises a molecular sieve synthesis basic unit or consists of molecular sieve colloidal particles which are not completely crystallized, and the crystal size of the molecular sieve is controlled by changing the composition, synthesis temperature and synthesis time of the colloidal molecular sieve precursor; the film thickness can be controlled by controlling the spin coating conditions; the heat treatment temperature of the colloidal molecular sieve precursor after being coated on the surface of the crystal oscillator is 40-80 ℃. The thickness of the molecular sieve membrane can be controlled by controlling the composition of the vapor phase and the reaction temperature and time.
The present invention will be described in more detail below with reference to examples.
Example 1
In this embodiment, the preparation method of the silicalite-1 type zeolite molecular sieve membrane on the surface of the quartz crystal oscillator comprises the following steps:
firstly, a colloidal zeolite precursor is coated on the surface of a quartz crystal oscillator substrate in a rotating mode. The preparation method of the colloidal zeolite precursor comprises the following steps: ethyl orthosilicate, tetrapropylammonium hydroxide and deionized water are mixed according to a molar ratio of 1:0.32:29, after the tetraethoxysilane is completely hydrolyzed, putting the solution into a reaction kettle for hydro-thermal synthesis, and carrying out hydro-thermal synthesis at 120 ℃ for 4 hours to obtain the zeolite precursor sol. And dropwise adding the zeolite precursor to the surface of a gold electrode of a quartz crystal oscillator, uniformly distributing precursor colloid on the surface of the gold electrode through a rotary coating machine, wherein the rotary coating speed is 2000 rpm/s, and the centrifugation time is 20 s. Fixing the quartz crystal oscillator substrate coated with the molecular sieve precursor at a position 3.5 cm away from the bottom of the reaction kettle by using a polytetrafluoroethylene support frame, and adding 5 ml of deionized water into the reaction kettle, wherein the volume of the reaction kettle is 100 ml. The temperature used for the vapor phase inversion was 170 ℃ for 24 hours, and the pressure was the autogenous pressure generated by vaporization of the solution. After the reaction is completed, the sample is repeatedly cleaned in deionized water at 100 ℃, and then cleaned for 20 minutes by using an ultrasonic cleaner with the frequency of 40Hz to remove residual solution and molecular sieve crystals weakly connected with the matrix. And (4) putting the cleaned sample into a drying box, and drying for 12 hours at the temperature of 100 ℃. After drying, the sample is roasted for 6 hours at 450 ℃ in a muffle furnace (the temperature rising speed is 2 ℃/minute, and the sample is cooled along with the furnace). As shown in fig. 2 (a) -2 (b), the thickness of the zeolite membrane was 500 nm and the size of the zeolite crystals was 100 nm.
Example 2
In this embodiment, the preparation method of the zeolite molecular sieve membrane on the surface of the zirconia crystal oscillator comprises the following steps:
firstly, surface modification is carried out on a foam silicon carbide carrier by utilizing a cationic polymer, and the specific process comprises the following steps: the foamed silicon carbide support was immersed in a 50wt% solution of tetraethylammonium hydroxide for 2 hours. Then, the surface of the gold electrode of the zirconia crystal oscillator substrate is coated with colloidal zeolite precursor in a rotating mode. The preparation method of the colloidal zeolite precursor comprises the following steps: ethyl orthosilicate, sodium metaaluminate, tetraethyl ammonium hydroxide and deionized water are mixed according to a molar ratio of 1:0.5:0.5:20 and mixing. And after the tetraethoxysilane is completely hydrolyzed, putting the solution into a reaction kettle, and carrying out hydro-thermal synthesis at 140 ℃ for 48 hours to prepare a precursor of the beta molecular sieve. And dropwise adding the zeolite precursor to the surface of a gold electrode of a zirconia crystal oscillator, uniformly distributing precursor colloid on the surface of the gold electrode through a rotary coating machine, wherein the rotary coating speed is 8000 rpm, and the centrifugation time is 20 seconds. The zirconia crystal oscillator substrate coated with the molecular sieve precursor is fixed at a position 3.5 cm away from the bottom of the reaction kettle by a polytetrafluoroethylene support frame, 5 ml of tetrapropylammonium hydroxide is added into the reaction kettle, and the volume of the reaction kettle is 100 ml. The temperature used for the vapor phase inversion was 170 ℃ for 24 hours, and the pressure was the autogenous pressure generated by vaporization of the solution. After the reaction is completed, the sample is repeatedly cleaned in deionized water at 100 ℃, and then cleaned for 20 minutes by using an ultrasonic cleaner with the frequency of 40Hz to remove residual solution and molecular sieve crystals weakly connected with the matrix. And (4) putting the cleaned sample into a drying box, and drying for 12 hours at the temperature of 100 ℃. After drying, the sample is roasted for 6 hours at 450 ℃ in a muffle furnace (the temperature rise speed is 2 ℃/minute, and the furnace is cooled). As shown in fig. 2 (a) -2 (b), the thickness of the zeolite membrane was 200 nm and the size of the zeolite crystals was 50 nm.
Example 3
In this embodiment, the method for preparing the Y-type zeolite molecular sieve film on the surface of the monocrystalline silicon crystal oscillator comprises:
firstly, ethyl orthosilicate, aluminum isopropoxide, sodium hydroxide, tetramethylammonium hydroxide and deionized water are mixed according to a molar ratio of 1:0.6:0.006:0.8:100, and mixing. After the tetraethoxysilane is completely hydrolyzed, the solution is placed in a reaction kettle, and is hydrothermally synthesized for 24 hours at the temperature of 95 ℃ to prepare a superfine Y molecular sieve precursor with the granularity of 50 nanometers. And dropwise adding the zeolite precursor to the surface of a gold electrode of a quartz crystal oscillator, uniformly distributing precursor colloid on the surface of the gold electrode through a rotary coating machine, wherein the rotary coating speed is 1000 revolutions per second, and the centrifugation time is 30 seconds. And fixing the monocrystalline silicon crystal oscillator coated with the molecular sieve precursor at a position 3.5 cm away from the bottom of the reaction kettle by using a polytetrafluoroethylene support frame, and adding 1 ml of deionized water into the reaction kettle, wherein the volume of the reaction kettle is 100 ml. The temperature used for the vapor phase inversion was 170 ℃ for 24 hours, and the pressure was the autogenous pressure generated by vaporization of the solution. After the reaction is completed, the sample is repeatedly cleaned in deionized water at 100 ℃, and then cleaned for 20 minutes by using an ultrasonic cleaner with the frequency of 40Hz to remove residual solution and molecular sieve crystals weakly connected with the matrix. And (4) putting the cleaned sample into a drying box, and drying for 12 hours at the temperature of 100 ℃. After drying, the sample is roasted for 6 hours at 450 ℃ in a muffle furnace (the temperature rising speed is 2 ℃/minute, and the sample is cooled along with the furnace). As shown in fig. 2 (a) -2 (b), the thickness of the zeolite membrane was 800 nm and the size of the zeolite crystals was 200 nm.
The results of the examples show that the molecular sieve membrane can be positioned and grown on the surface of the quartz crystal oscillator gold electrode, the molecular sieve membrane is firmly combined with the gold electrode, the interface bonding strength is more than 3MPa, and the thickness of the molecular sieve membrane is 100 nanometers to 1 micrometer. The adsorption of characteristic gas is realized by utilizing the pore structure of a specific type of molecular sieve and the action of hydrophilic and hydrophobic properties and an internal electric field, and the size of the adsorption quantity is determined by the change of crystal oscillation frequency. The quartz crystal oscillator loaded with the molecular sieve membrane has good weight sensitivity and has good application prospect in the aspect of atmospheric organic gas detection.
Claims (7)
1. A crystal oscillator surface molecular sieve membrane material is characterized in that gold electrodes are plated on two surfaces of a crystal oscillator substrate, a molecular sieve membrane only exists on the surface of the gold electrode of the crystal oscillator substrate, the thickness of the molecular sieve membrane is less than 1 micron, and the interface bonding force between the molecular sieve membrane and the gold electrode is more than 3MPa;
firstly, coating colloidal molecular sieve precursor or mixed slurry of the colloidal molecular sieve precursor and nano molecular sieve powder on the surface of a gold electrode of a crystal oscillator substrate in a rotating manner and carrying out heat treatment; then, converting the molecular sieve precursor into a molecular sieve crystal through vapor phase treatment, and realizing firm combination between the coating and the carrier; the colloidal molecular sieve precursor comprises a molecular sieve synthesis basic unit or consists of molecular sieve colloidal particles which are not completely crystallized, the crystal size of the molecular sieve is controlled by changing the composition, the synthesis temperature and the synthesis time of the colloidal molecular sieve precursor, and the film thickness is controlled by controlling the spin coating condition; after the colloidal molecular sieve precursor is coated on the surface of a gold electrode of a crystal oscillator substrate, the heat treatment temperature is 40-80 ℃, and the thickness of a molecular sieve film is controlled by controlling the steam phase composition, the reaction temperature and the reaction time;
the synthesis method of the colloidal molecular sieve precursor comprises the following steps:
(1) Mixing a silicon source, an aluminum source, a template agent and deionized water in proportion, wherein the molar ratio of the silicon source to the aluminum source to the template agent to the deionized water is 1:0.001 to 0.2:0 to 1.0:5 to 200;
(2) Hydrothermal treatment: after the silicon source is completely hydrolyzed, aging the solution at 40 +/-5 ℃ for 24-96 hours to form a colloidal molecular sieve precursor;
(3) Adjusting the colloid concentration: adding an organic solvent into the colloidal molecular sieve precursor: ethanol, methanol, isopropanol or tween, and the colloidal molecular sieve precursor is diluted to the concentration of 5-50 wt%.
2. The crystal oscillator surface molecular sieve membrane material according to claim 1, wherein the crystal oscillator substrate is made of a piezoelectric ceramic substrate: quartz, silicon, zirconia, or barium titanate.
3. The crystal oscillator surface molecular sieve membrane material according to claim 1, wherein the molecular sieve is a ZSM-5 type molecular sieve, a beta type molecular sieve, a Y type molecular sieve, an SSZ-13 type molecular sieve, an A type molecular sieve or the molecular sieve subjected to modification treatment, and the molecular sieve modification method is noble metal loading modification, alkali metal modification or alkaline earth metal modification.
4. The crystal oscillator surface molecular sieve membrane material according to claim 1 or 3, wherein the molecular sieve membrane has a thickness of 50 to 1000 nm.
5. The crystal oscillator surface molecular sieve membrane material according to claim 1, wherein in the preparation process of the colloidal molecular sieve precursor, the silicon source is one or more than two of tetraethoxysilane, silica sol or white carbon black, and the aluminum source is one or more than two of sodium metaaluminate, aluminum nitrate, aluminum sulfate, aluminum isopropoxide or aluminum foil; when preparing a colloidal ZSM-5 molecular sieve precursor, adopting tetrapropyl ammonium hydroxide, tetrapropyl ammonium bromide or a mixture of the tetrapropyl ammonium hydroxide and the tetrapropyl ammonium bromide as a template agent; when the colloidal state beta molecular sieve precursor is prepared, tetraethyl ammonium hydroxide, tetraethyl ammonium bromide or a mixture of tetraethyl ammonium hydroxide and tetraethyl ammonium bromide is used as a template agent; when preparing colloidal Y-type molecular sieve precursor, tetramethyl ammonium hydroxide, tetramethyl ammonium bromide or their mixture is used as template agent.
6. The crystal oscillator surface molecular sieve membrane material according to claim 1, wherein for the preparation of the nano molecular sieve membrane material on the surface of the gold electrode of the crystal oscillator substrate, the used vapor phase is pure water or tetrapropylammonium hydroxide aqueous solution or ethylenediamine and triethylamine aqueous solution, the reaction temperature is 100-250 ℃, and the reaction time is 3-200 hours.
7. The application of the crystal oscillator surface molecular sieve membrane material as claimed in any one of claims 1 to 6, wherein the adsorption of characteristic gas is realized by utilizing the pore structure and the hydrophilic-hydrophobic and internal electric field effects of a specific type of molecular sieve, and the magnitude of the adsorption capacity is determined by the change of the crystal oscillator frequency.
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