CN110759351A - 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 PDF

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CN110759351A
CN110759351A CN201810832274.5A CN201810832274A CN110759351A CN 110759351 A CN110759351 A CN 110759351A CN 201810832274 A CN201810832274 A CN 201810832274A CN 110759351 A CN110759351 A CN 110759351A
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molecular sieve
crystal oscillator
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precursor
membrane material
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张劲松
矫义来
郭兴
杨生胜
薛玉雄
庄建宏
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Institute of Metal Research of CAS
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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 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.

Description

Crystal oscillator surface molecular sieve membrane material and preparation method and application thereof
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 pore canals of the molecular sieve.
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 the 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 3 MPa.
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 membrane material on the surface of the crystal oscillator 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 molecular sieve modification method 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: 0.001-0.2: 0 to 1.0 (the template is generally 0.1 to 1.0): 5-200;
(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: and ethanol, methanol, isopropanol or tween, and diluting the colloidal molecular sieve precursor to a concentration of 5-50 wt%.
The preparation method of the crystal oscillator surface molecular sieve membrane material comprises the steps of in the preparation process of a colloidal molecular sieve precursor, enabling a silicon source to be one or more of ethyl orthosilicate, silica sol or white carbon black, enabling an aluminum source to be one or more of sodium metaaluminate, aluminum nitrate, aluminum sulfate, aluminum isopropoxide or aluminum foil, enabling tetrapropylammonium hydroxide and tetrapropylammonium bromide or a mixture of the tetrapropylammonium hydroxide and the tetrapropylammonium bromide to serve as a template agent when the colloidal ZSM-5 molecular sieve precursor is prepared, enabling tetraethylammonium hydroxide and tetraethylammonium bromide or a mixture of the tetraethylammonium hydroxide and the tetraethylammonium bromide to serve as a template agent when the colloidal β molecular sieve precursor is prepared, and enabling tetramethylammonium hydroxide and tetramethylammonium bromide or a mixture of the tetramethylammonium hydroxide and the tetramethylammonium bromide to serve as the template agent when the colloidal Y-type molecular sieve precursor is prepared.
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 invention has the following beneficial effects and specific innovation points:
(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 3 MPa.
(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 10-8g/cm2。
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) show the morphology 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 electric field and oscillation frequency of a 15MHz piezoelectric quartz crystal. Fig. 3(a) is a perspective view, and fig. 3(b) is a front view. Reference number in the figure, 1 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 3 MPa. The crystal oscillator substrate is made of quartz, silicon, or ceramic substrates such as zirconium oxide and barium titanate. 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 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 example, the preparation method of the β -type zeolite molecular sieve membrane on the zirconia crystal oscillator surface:
firstly, utilizing cationic polymer to modify the surface of a foam silicon carbide carrier, and specifically, soaking the foam silicon carbide carrier in 50 wt% tetraethylammonium hydroxide solution for 2 hours, then, rotationally coating colloidal zeolite precursor on the surface of a gold electrode of a zirconia crystal oscillator substrate, wherein the colloidal zeolite precursor is prepared by mixing ethyl orthosilicate, sodium metaaluminate, tetraethylammonium hydroxide and deionized water according to a molar ratio of 1: 0.5: 0.5: 20, placing the solution in a reaction kettle after the ethyl orthosilicate is completely hydrolyzed, carrying out hydrothermal synthesis for 48 hours at 140 ℃ to prepare β molecular sieve precursor, dropwise adding the zeolite precursor on the surface of the gold electrode of the zirconia crystal oscillator, uniformly distributing the colloid on the surface of the gold electrode through a rotational coating machine, wherein the rotational coating speed is 8000 rpm, the centrifugal time is 20 seconds, fixing the zirconia crystal oscillator substrate coated with the molecular sieve precursor at a position 3.5 cm from the bottom of the reaction kettle by using a polytetrafluoroethylene support frame, adding 5 ml tetrapropylammonium hydroxide into the reaction kettle, the volume is 100. the sample, the sample is cleaned under the conditions of 100 ℃ steam phase temperature, the temperature is 100 minutes, the drying temperature is 200 minutes, the sample is dried under the conditions that the drying temperature is 100 ℃ and the temperature of the drying is 100 minutes, the sample is 100 minutes, the drying process is 100 minutes, the sample is 100 minutes, the drying process is completed by using a drying process, the drying process is 100 ℃ is shown in a drying process, the drying process is completed by using a drying process is 100-drying process, the drying process.
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. Fixing the molecular sieve precursor-coated monocrystalline silicon crystal oscillator 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 (9)

1. The molecular sieve membrane material on the surface of the crystal oscillator is characterized in that gold electrodes are plated on two surfaces of a crystal oscillator substrate, the molecular sieve membrane is only present 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 3 MPa.
2. The crystal oscillator surface molecular sieve membrane material according to claim 1, wherein the crystal oscillator substrate material is 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 thickness of the molecular sieve membrane is 50-1000 nm.
5. The method for preparing the molecular sieve membrane material on the surface of the crystal oscillator according to any one of claims 1 to 4, characterized in that firstly, colloidal molecular sieve precursors or mixed slurry of the colloidal molecular sieve precursors and nano molecular sieve powder are coated on the surface of the gold electrode of the crystal oscillator substrate in a rotating manner and heat treatment is carried out; 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.
6. The method for preparing the crystal oscillator surface molecular sieve membrane material according to claim 5, wherein the synthesis method of the colloidal molecular sieve precursor is as follows:
(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: 0.001-0.2: 0-1.0: 5-200;
(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: and ethanol, methanol, isopropanol or tween, and diluting the colloidal molecular sieve precursor to a concentration of 5-50 wt%.
7. The method for preparing the molecular sieve membrane material on the surface of the crystal oscillator according to claim 6, wherein in the preparation process of the colloidal molecular sieve precursor, the silicon source is one or more of ethyl orthosilicate, silica sol or white carbon black, the aluminum source is one or more of sodium metaaluminate, aluminum nitrate, aluminum sulfate, aluminum isopropoxide or aluminum foil, tetrapropylammonium hydroxide, tetrapropylammonium bromide or a mixture of the tetrapropylammonium hydroxide and the tetrapropylammonium bromide is used as a template agent when the colloidal ZSM-5 molecular sieve precursor is prepared, tetraethylammonium hydroxide, tetraethylammonium bromide or a mixture of the tetraethylammonium hydroxide and the tetraethylammonium bromide is used as a template agent when the colloidal β molecular sieve precursor is prepared, and tetramethylammonium hydroxide, tetramethylammonium bromide or a mixture of the tetramethylammonium hydroxide and the tetramethylammonium bromide is used as a template agent when the colloidal Y-type molecular sieve precursor is prepared.
8. The method for preparing the molecular sieve membrane material on the surface of the crystal oscillator according to claim 5, wherein the vapor phase used for preparing the nano molecular sieve membrane material on the surface of the gold electrode of the crystal oscillator substrate is pure water or an aqueous solution of tetrapropylammonium hydroxide or an aqueous solution of ethylenediamine and triethylamine, the reaction temperature is 100-250 ℃, and the reaction time is 3-200 hours.
9. The use of the molecular sieve membrane material for crystal oscillator surfaces according to any one of claims 1 to 4, wherein the adsorption of characteristic gases 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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