CN109883877A - Quartz crystal microbalance and humidity sensor based on metal-organic framework material - Google Patents
Quartz crystal microbalance and humidity sensor based on metal-organic framework material Download PDFInfo
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Abstract
The present invention provides a kind of quartz crystal microbalance, including quartz crystal matrix, electrode and humidity sensitive layer, the electrode is arranged at least part of the quartz crystal matrix, which is arranged at least part of the electrode, and wherein the humidity sensitive layer includes metal-organic framework material.The metal-organic framework material is the combination of one or more of Cu-BTC, Fe-BTC, MOF-801 and MOF-801P.The quartz crystal microbalance still has very strong holding capacity to hydrone under low moisture environments since humidity sensitive layer includes metal-organic framework material, and is much larger than other molecules in the selectivity to hydrone.The present invention also provides the quartz crystal microbalance humidity sensor including the quartz crystal microbalance, the moisture content in low moisture environments can detecte.Quartz crystal microbalance and quartz crystal microbalance humidity sensor preparation method of the invention is simple, at low cost.
Description
Technical field
The present invention relates to moisture measurement technical fields, and in particular to one kind is based on the stone of metal-organic framework material (MOF)
English crystal microbalance and a kind of humidity sensor including the quartz crystal microbalance.
Background technique
Humidity is the physical quantity for indicating the sub- content of atmosphere moisture is how many, indicates the dry and wet degree of atmosphere.Moisture measurement
It is ceased with the industrial productions such as humid control and scientific research, environmental monitoring, food and drug and circulation and daily life
Manner of breathing closes.
Humidity sensor is the instrument for measuring humidity, can be divided into conventional moisture sensor and low humidity sensor (dew point
Instrument).Conventional moisture sensor is generally used for the relative humidity (RH) in production and life in detection gas, such as wet and dry bulb humidity
Meter, mechanical hygrometer and macromolecule membrane hygrometer.Low humidity sensor is generally used for the micro-moisture in detection gas and (is lower than
The moisture content of 100ppm), the temperature dew point (DP) when generally using ppm or sample gas being cooled to condensation droplet is list
Position, therefore industrial is usually dew point hygrometer by low humidity scales.The micro-moisture measurement of ppm magnitude even ppb magnitude exists
There is a large amount of application in the fields such as semiconductors manufacture, the storage of food or agricultural products, the storage and medicine preparation of gas and fuel.
Some very important industrial products need to measure low-down moisture content.For example, the humidity of transformer oil requires 5-
25ppm, the humidity of plutonium element pallet require 4-30ppm, and the humidity of integrated circuit (IC) manufacture requires 10-100ppm.Inspection at present
The method for surveying micro-moisture mainly has gravimetric method, electrolysis method, Rong Zufa, Cold Mirrors method and vibration frequency method.
Typical instrument using vibration frequency method measurement humidity is quartz crystal microbalance (quartz crystal
Microbalance, QCM) humidity sensor.This sensor includes with humidity sensitive thin film and the QCM humidity without humidity sensitive thin film
Sensor.In general, the QCM humidity sensor with humidity sensitive thin film plates one layer of electrode using quartz crystal as matrix, on crystal two sides,
Then one layer of humidity sensitive thin film is plated again on the electrode.After humidity sensitive thin film moisture absorption, the quality of plane of crystal be will increase, the vibration frequency of crystal
Rate can accordingly decline.Moisture measurement may be implemented by the relationship of crystal vibration frequency and quality, have high sensitivity, precision high
The advantages of, it can reach the mass-basis response sensitivity of nanogram level.Humidity-sensitive material is the pass for preparing the humidity sensitive thin film of QCM humidity sensor
Key material.Good humidity-sensitive material should have hypersensitivity, repeatability, quick response and short recovery time, small hysteresis,
The properties such as low energy consumption.Organic material as humidity-sensitive material usually has a relatively good performance in high humidity, but the low humidity of ppm magnitude
Environment does not often respond to.Therefore, the humidity to measure low moisture environments, it is necessary to the new humidity-sensitive material of development and application.
Summary of the invention
The purpose of the present invention is to provide a kind of quartz crystal microbalance, which has in low moisture environments
It is of the invention further objective is that providing a kind of including the quartz crystal microbalance down with the humidity-sensitive material of good response
Quartz crystal microbalance humidity sensor can detecte the moisture content in low moisture environments.
Therefore, in a first aspect, the present invention provides a kind of quartz crystal microbalance, which includes quartz
Crystal matrix, electrode and humidity sensitive layer, the electrode are arranged at least part of the quartz crystal matrix, and humidity sensitive layer setting exists
In at least part of the electrode, wherein the humidity sensitive layer includes metal-organic framework material.
The metal-organic framework material is one or more of Cu-BTC, Fe-BTC, MOF-801 and MOF-801P's
Combination.
Specifically, in some embodiments of the present invention, which is Cu-BTC；Of the invention
In other embodiments, which is Fe-BTC；In other embodiment of the invention, the metal
Organic framework materials are MOF-801；In some other embodiments of the invention, which is MOF-
801P；In other embodiment of the invention, the metal-organic framework material be Cu-BTC, Fe-BTC, MOF-801 and
Two kinds or more of combinations in MOF-801P.
The humidity sensitive layer comprising metal-organic framework material can be used at least one that the electrode is arranged in suitable mode
On point.
In some embodiments of the present invention, which can be by coating the gold at least part of the electrode
Belong to organic framework materials and is arranged at least part of the electrode.Spin coater can be used by the metal-organic framework material
On surface coated in the quartz crystal microbalance, to be arranged at least part of the electrode.
In other embodiments of the invention, which can be by giving birth in situ at least part of the electrode
Long Cu-BTC or Fe-BTC and Cu-BTC or Fe-BTC are set at least part of the electrode.It can be by should
Quartz crystal microbalance, which is placed in Cu-BTC and is perhaps handled in the precursor solution of Fe-BTC, keeps Cu-BTC or Fe-BTC in situ
It is grown on the surface of the quartz crystal microbalance, to make Cu-BTC or Fe-BTC that at least part of the electrode be arranged in
On.
In some preferred embodiments of the invention, the quartz crystal matrix of the quartz crystal microbalance includes two
Opposite surface is provided with an electrode on each quartz crystal matrix surface, one layer of humidity sensitive layer is provided on each electrode, should
Humidity sensitive layer includes the combination of one or more of Cu-BTC, Fe-BTC, MOF-801 and MOF-801P.As specific reality
Scheme is applied, which can be quartz wafer, which can be electrode slice.
In of the invention one specific preferred embodiment, the humidity sensitive layer of the quartz crystal microbalance includes Cu-
BTC.In another specific preferred embodiment of the invention, which includes Fe-BTC.In another of the invention
In specific preferred embodiment, which includes MOF-801.In the specific preferred embodiment of another of the invention
In, which includes MOF-801P.
In of the invention one specific preferred embodiment, each electrode of the quartz crystal microbalance draws one
Lead, the lead are electrically connected with electrode formation.
In of the invention one specific preferred embodiment, which further includes pedestal, this draws
Line is fixedly connected with the pedestal and is fixedly supported on the quartz wafer on the pedestal.
In of the invention one specific preferred embodiment, which further includes shell, the shell
The quartz wafer for accommodating the pedestal and being fixedly supported on the pedestal.
In second aspect, the present invention provides a kind of quartz crystal microbalance humidity sensor, which includes this
The quartz crystal microbalance and signal acquisition circuit and signal processor of invention first aspect.
Signal acquisition circuit and signal processor generally in the art can be used, this is well known in the art.For example, right
In signal acquisition circuit, common oscillating circuit and phase-locked oscillation circuit can be used, common oscillating circuit is preferably used.Commonly
Oscillating circuit further includes the common oscillating circuit of Series FPB and parallel FPB, it is preferred to use the common oscillating circuit of tandem type.
Beneficial effects of the present invention
Quartz crystal microbalance of the invention uses novel humidity sensitive layer, wherein include metal-organic framework material,
Still there is very strong holding capacity to hydrone under low moisture environments, and is much larger than other molecules such as in the selectivity to hydrone
Carbon dioxide, nitrogen, oxygen or hydro carbons still have response to hydrone in the low moisture environments of ppm magnitude.Therefore, by the present invention
Quartz crystal microbalance manufacture quartz crystal microbalance humidity sensor of the present invention can detecte the moisture in low moisture environments
Content.
Meanwhile quartz crystal microbalance of the invention can use existing quartz crystal microbalance, by coating or
Metal-organic framework material is arranged on the electrode of quartz crystal microbalance the method for growth in situ, and preparation method is simple, at
This is low.
Detailed description of the invention
Fig. 1 is the structural schematic diagram according to the quartz crystal microbalance (QCM) of embodiment of the present invention, wherein attached drawing mark
Note 1 indicates quartz crystal matrix, and 2 indicate electrode, and 3 indicate humidity sensitive layer, and 4 indicate contact conductor, and 5 indicate pedestal；
Fig. 2 is the structural schematic diagram according to the quartz crystal microbalance sensor of embodiment of the present invention；
Fig. 3 is that the frequency of the QCM humidity sensor with Cu-BTC humidity sensitive layer changes with the system dew point value and changed
Tendency chart；
Fig. 4 is that the frequency of the QCM humidity sensor with MOF-801P humidity sensitive layer changes with the system dew point value and changed
Tendency chart.
Specific embodiment
Below by specific embodiment combination attached drawing, invention is further described in detail.In the following embodiments and the accompanying drawings
In, many datail descriptions are in order to enable the application can be better understood.However, those skilled in the art can be without lifting an eyebrow
Recognize, part of feature is dispensed in varied situations, or can be by other elements, material, method institute
Substitution.In some cases, the relevant some operations of the application there is no display in the description or describe, this is to keep away
The core for exempting from the application is flooded by excessive description, and to those skilled in the art, these phases are described in detail
It closes operation not to be necessary, they can completely understand according to the general technology knowledge of description and this field in specification
Relevant operation.
It is formed respectively in addition, feature described in this description, operation or feature can combine in any suitable way
Kind embodiment.Meanwhile each step in method description or movement can also can be aobvious and easy according to those skilled in the art institute
The mode carry out sequence exchange or adjustment seen.Therefore, the various sequences in the description and the appended drawings are intended merely to clearly describe a certain
A embodiment is not meant to be necessary sequence, and wherein some sequentially must comply with unless otherwise indicated.
It is herein component institute serialization number itself, such as " first ", " second " etc., is only used for distinguishing described object,
Without any sequence or art-recognized meanings.And " connection ", " connection " described in the application, unless otherwise instructed, include directly and
It is indirectly connected with, couples.
Metal-organic framework material (metal organic frameworks, MOFs) is a kind of crystalline compound, be by
The two dimension or three-dimensional structure that metal ion or metal ion cluster and organoligand coordination are formed, therefore MOFs is a kind of height
The two dimension or three-dimensional coordination polymer of crystallization.MOFs has lightweight, high voidage, high-specific surface area and duct adjustable etc. special
Property, it is wide that these characteristics have it in fields such as gas storage, chemical catalysis, substance absorption, substance separation and chemical sensors
General application potential.
MOFs is found to be potential Water Molecular Adsorption material since porosity and surface area are big.As non-limiting example
Son, studies have found that, Cu-BTC and Fe-BTC MOF material has water absorption, and also has adsorptive selectivity.For example,
Ahmed Rezk et al. (" Characterisation of metal organic frameworks for adsorption
Cooling ", International Journal of Heat and Mass Transfer, Volume 55, Issues
2526, December 2012, Pages 7366-7374) the measuring water absorption of Cu-BTC and Fe-BTC.For another example,
Juan Manuel Castillo et al. (" Understanding Water Adsorption in Cu-BTC Metal-
Organic Frameworks ", J.Phys.Chem.C, 2008,112 (41), pp 15934-15939) it has studied in Cu-BTC
Water absorption behavior, discovery water other molecules such as titanium dioxide is unexpectedly greater than to the affinity of the metal center in Cu-BTC
The affinity of carbon, nitrogen, oxygen or hydro carbons to metal center.As other non-limitative example, M.V.Solovyeva et al.
(“MOF-801 as a promising material for adsorption cooling:Equilibrium and
Dynamics of water adsorption ", Energy Conversion and Management, Volume 174,15
October 2018, Pages 356-363) elaborate that the good water absorption matter of MOF-801 can be used for adsorbing cooling.It is true
On, the above-mentioned research about Cu-BTC and Fe-BTC is also related to absorption cooling.
The inventors discovered that MOFs still has very strong holding capacity to hydrone under low moisture environments.Therefore, of the invention
People develops by a large amount of research using MOFs as the humidity sensor of the ppm magnitude of humidity-sensitive material, opens the new of MOFs
Application field.
The present invention is illustrated below by way of non-limiting embodiment.
Embodiment 1
The present embodiment coats Cu-BTC on the surface quartz crystal microbalance (QCM).For this purpose, preparing one without wet sensitive
The quartz crystal microbalance of film, which is 8.6mm and frequency is 5MHz, including a quartz wafer
With two gold electrode pieces on two surfaces for being located at the quartz wafer；Meanwhile Cu-BTC is prepared for coating.
To prepare Cu-BTC, 5g trimesic acid (H is weighed3BTC it) is mixed with 10ml DMSO, ultrasonic dissolution.It will be resulting
Solution is cooling, is slowly added to 4.46g Cu (NO3)2·3H2O, ultrasonic dissolution obtain blue-tinted transparent solution.The solution is transferred to
In 25ml water heating kettle (Zhengzhou Kodak, ZZKD KH-25), 120 DEG C of heated at constant temperature for 24 hours, obtain final product Cu-BTC.
It is solute, dehydrated alcohol as solvent using polyvinyl alcohol (PVA), prepares 0.5%PVA/ ethanol solution.It weighs
The Cu-BTC of the above-mentioned preparation of 0.1g is dissolved in the 0.5%PVA solution of the above-mentioned preparation of 10ml, and application of mixture is made.Use spin coating
The application of mixture is coated on the surface of the quartz crystal microbalance two sides by machine (department's pleasure, TB-616), and it is wet to form Cu-BTC
Then photosensitive layer is dried for 24 hours in drying box, then connects contact conductor and pedestal, the quartz that Cu-BTC is coated on surface is obtained
Crystal microbalance, as Fig. 1 is illustrated.Finally, connecting common oscillating circuit and signal processor again, final assembling is had
There is quartz crystal microbalance (QCM) humidity sensor of Cu-BTC humidity sensitive layer, as Fig. 2 is illustrated.
Embodiment 2
The present embodiment coats Fe-BTC on the surface quartz crystal microbalance (QCM).For this purpose, preparing one without wet sensitive
The quartz crystal microbalance of film, which is 8.6mm and frequency is 5MHz, including a quartz wafer
With two gold electrode pieces on two surfaces for being located at the quartz wafer；Meanwhile Fe-BTC is prepared for coating.
To prepare Fe-BTC, 2g FeCl is weighed3·6H2O and 1.55g trimesic acid (H3BTC), it is dissolved in 5ml diformazan
In base formamide (DMF).Resulting solution mixture is transferred to stainless steel water heating kettle (the Zhengzhou Kodak of 15ml Teflon liner
KDSR-15 in), 150 DEG C of heated at constant temperature for 24 hours, then connect contact conductor and pedestal, obtain red Fe-BTC gel.Then,
The gel is alternately cleaned several times in DMF and alcohol and is centrifuged removal solvent, finally in 60 DEG C of vacuum drying 6h, is obtained final
Product Fe-BTC.
It is solute, dehydrated alcohol as solvent using polyvinyl alcohol (PVA), prepares 0.5%PVA/ ethanol solution.It weighs
The Fe-BTC of the above-mentioned preparation of 0.1g is dissolved in the 0.5%PVA solution of the above-mentioned preparation of 10ml, and application of mixture is made.Use spin coating
The application of mixture is coated on the surface of the quartz crystal microbalance two sides by machine (department's pleasure, TB-616), and it is wet to form Fe-BTC
Then photosensitive layer is dried for 24 hours in drying box, then connects contact conductor and pedestal, the quartz that Fe-BTC is coated on surface is obtained
Crystal microbalance, as Fig. 1 is illustrated.Finally, connecting common oscillating circuit and signal processor again, final assembling is had
There is quartz crystal microbalance (QCM) humidity sensor of Fe-BTC humidity sensitive layer, as Fig. 2 is illustrated.
Embodiment 3
The present embodiment coats MOF-801 on the surface quartz crystal microbalance (QCM).For this purpose, preparing one without wet
The quartz crystal microbalance of sensitive film, which is 8.6mm and frequency is 5MHz, including a quartz-crystal
Piece and two gold electrode pieces being located on two surfaces of the quartz wafer；Meanwhile MOF-801 is prepared for coating.
To prepare MOF-801,1.2g fumaric acid and 3.2g ZrOCl are weighed2·8H2O is dissolved in DMF and formic acid
In mixed solvent (40ml DMF, 14ml formic acid).Resulting mixture is transferred to water heating kettle (upper sea cowry logical sequence, GFK-10-500)
In, 120 DEG C of heated at constant temperature for 24 hours.Resulting product is washed three times with DMF, is then impregnated three days in methyl alcohol again.Finally true
Aerial 150 DEG C of heated at constant temperature for 24 hours, obtain final product MOF-801.
It is solute, dehydrated alcohol as solvent using polyvinyl alcohol (PVA), prepares 0.5%PVA/ ethanol solution.It weighs
The MOF-801 of the above-mentioned preparation of 0.1g is dissolved in the 0.5%PVA solution of the above-mentioned preparation of 10ml, and application of mixture is made.Use rotation
The application of mixture is coated on the surface of the quartz crystal microbalance two sides by painting machine (department's pleasure, TB-616), forms MOF-801
Then humidity sensitive layer is dried for 24 hours in drying box, then connects contact conductor and pedestal, the stone that MOF-801 is coated on surface is obtained
English crystal microbalance, as Fig. 1 is illustrated.Finally, connecting common oscillating circuit and signal processor again, final assembling is obtained
Quartz crystal microbalance (QCM) humidity sensor with MOF-801 humidity sensitive layer, as Fig. 2 is illustrated.
Embodiment 4
The present embodiment coats MOF-801P on the surface quartz crystal microbalance (QCM).For this purpose, preparing one without wet
The quartz crystal microbalance of sensitive film, which is 8.6mm and frequency is 5MHz, including a quartz-crystal
Piece and two gold electrode pieces being located on two surfaces of the quartz wafer；Meanwhile MOF-801P is prepared for coating.
To prepare MOF-801P, by 6g fumaric acid and 16g ZrOCl2·8H2O is dissolved in DMF and the mixing of formic acid is molten
In agent (200ml DMF, 70ml formic acid).Then, resulting mixture is placed in 500ml water heating kettle (upper sea cowry logical sequence GFK-10-
500) in, in 130 DEG C of heated at constant temperature 6h.Using (0.2 μm) filtering reactant of nylon micro porous filter membrane, white precipitate is obtained.It will
White precipitate is cleaned three times with DMF and methanol respectively, and then soaking flushing three days in anhydrous DMF, then soak in alcohol again
Bubble three days.Finally 150 DEG C of heated at constant temperature for 24 hours, obtain final product MOF-801P in a vacuum.
It is solute, dehydrated alcohol as solvent using polyvinyl alcohol (PVA), prepares 0.5%PVA/ ethanol solution.It weighs
The MOF-801P of the above-mentioned preparation of 0.1g is dissolved in the 0.5%PVA solution of the above-mentioned preparation of 10ml, and application of mixture is made.Use rotation
The application of mixture is coated on the surface of the quartz crystal microbalance two sides by painting machine (department's pleasure, TB-616), forms MOF-
Then 801P humidity sensitive layer is dried for 24 hours in drying box, then connects contact conductor and pedestal, obtain being coated with MOF- on surface
The quartz crystal microbalance of 801P, as Fig. 1 is illustrated.Finally, connecting common oscillating circuit and signal processor again, finally
Assembling obtains quartz crystal microbalance (QCM) humidity sensor with MOF-801P humidity sensitive layer, as Fig. 2 is illustrated.
Embodiment 5
The present embodiment grows Cu-BTC in quartz crystal microbalance (QCM) surface in situ.For this purpose, preparing one without wet
The quartz crystal microbalance of sensitive film, which is 8.6mm and frequency is 5MHz, including a quartz-crystal
Piece and two gold electrode pieces being located on two surfaces of the quartz wafer；Meanwhile preparing 50ml 1.0mM copper acetate (Cu
(OAc)2)/ethanol solution and 50ml 0.1mM 1,3,5- trimesic acid (H3BTC)/ethanol solution, and by two kinds
Solution is placed in the insulating box (one is permanent, 9123A) that temperature is 50 DEG C.
The quartz crystal microbalance is immersed in copper acetate/ethanol solution and is handled 20 minutes, is then taken out, with nothing
Water-ethanol rinses 10 minutes, to remove excessive acetic acid copper reagent from the quartz crystal microbalance surface；Then, by the quartz
Crystal microbalance is immersed in 1, handles 20 minutes in 3,5- benzenetricarboxylic acids/ethanol solution, then takes out, floated with dehydrated alcohol
It washes 10 minutes, to remove excessive 1,3,5- benzenetricarboxylic acid reagents from the quartz crystal microbalance surface.This is a processing
Circulation.
After first processing cycle, initiation layer is covalently attached to the electrode surface of the quartz crystal microbalance, forms the
One Cu-BTC layers.In subsequent processing cycle, the solvation copper metal ion and previous Cu-BTC layers of BTC newly introduced occurs
Complexation reaction, so with the H that newly introduces3Complexation reaction occurs for BTC.Circulation per treatment increases Cu-BTC thickness controllably.
It can be by controlling soaking time, the Cu-BTC growth rate of temperature and solution concentration to keep constant.With Cu-BTC thickness
Increase, the vibration frequency of the quartz crystal microbalance can become smaller.Every 20 processing cycles test the primary quartz crystal microbalance
Frequency variation, according to frequency change determination reach target thickness.For example it is assumed that the initial frequency of QCM is 5000000Hz,
Target thickness is frequency variation 30000Hz, when measurement frequency is 4970000Hz, has reached target thickness with regard to explanation.
After completing the growth of Cu-BTC humidity sensitive layer, by the quartz crystal microbalance with Cu-BTC humidity sensitive layer first in saturation first
Handle in alcohol KOH solution, then rinsed with dehydrated alcohol, it is then dry in dry nitrogen air-flow, then in a nitrogen atmosphere in
150 DEG C are toasted 24 hours, the quartz crystal microbalance that growth in situ on surface has Cu-BTC are obtained, as Fig. 1 is illustrated.Most
Afterwards, then common oscillating circuit and signal processor are connected, final assembling obtains having the micro- day of the quartz crystal of Cu-BTC humidity sensitive layer
Flat (QCM) humidity sensor, as Fig. 2 is illustrated.
Embodiment 6
The present embodiment grows Fe-BTC in quartz crystal microbalance (QCM) surface in situ.For this purpose, preparing one without wet
The quartz crystal microbalance of sensitive film, which is 8.6mm and frequency is 5MHz, including a quartz-crystal
Piece and two gold electrode pieces being located on two surfaces of the quartz wafer；Meanwhile preparing 50ml 1.0mM iron chloride
(FeCl3·6H2O)/ethanol solution and 50ml 0.1mM 1,3,5- trimesic acid (H3BTC)/ethanol solution, and
Two kinds of solution are placed in the insulating box (one is permanent, 9123A) that temperature is 50 DEG C.
The quartz crystal microbalance is immersed in iron chloride/ethanol solution and is handled 20 minutes, is then taken out, with nothing
Water-ethanol rinses 10 minutes, to remove excessive chlorination ferron from the quartz crystal microbalance surface；Then, by the quartz
Crystal microbalance is immersed in 1, handles 20 minutes in 3,5- benzenetricarboxylic acids/ethanol solution, then takes out, floated with dehydrated alcohol
It washes 10 minutes, to remove excessive 1,3,5- benzenetricarboxylic acid reagents from the quartz crystal microbalance surface.This is a processing
Circulation.
In the same manner as in Example 5, increase Fe-BTC thickness controllably by multiple processing cycles.When can be impregnated by control
Between, the Fe-BTC growth rate of temperature and solution concentration to keep constant.Every 20 processing cycles test the primary quartz crystal
The frequency of micro- balance changes, and reaches target thickness according to frequency change determination.
After completing the growth of Fe-BTC humidity sensitive layer, by the quartz crystal microbalance with Fe-BTC humidity sensitive layer first in saturation first
Handle in alcohol KOH solution, then rinsed with dehydrated alcohol, it is then dry in dry nitrogen air-flow, then in a nitrogen atmosphere in
150 DEG C are toasted 24 hours, the quartz crystal microbalance that growth in situ on surface has Fe-BTC are obtained, as Fig. 1 is illustrated.Most
Afterwards, then common oscillating circuit and signal processor are connected, final assembling obtains having the micro- day of the quartz crystal of Fe-BTC humidity sensitive layer
Flat (QCM) humidity sensor, as Fig. 2 is illustrated.
Test case
Quartz crystal microbalance (QCM) humidity sensor with Cu-BTC humidity sensitive layer prepared by this test case embodiment 1
Quartz crystal microbalance (QCM) humidity sensor with MOF-801P humidity sensitive layer prepared by device and embodiment 4 is test sensing
Device tests the hygrometric ability of QCM humidity sensor of the invention.
Test sensor is welded to the present inventor from the dew point transmitter ground, dew point transmitter is then put into dew point
In generation and calibration system (Michell DCS100), to test its frequency with the variation of system dew point.- 30 in the system
DEG C, -40 DEG C, -50 DEG C, -60 DEG C, keep respectively about 1 hour under -70 DEG C and -80 DEG C of dew points, observe humidity sensor frequency with dew
The response of point.
Fig. 3 is that the frequency of the QCM humidity sensor with Cu-BTC humidity sensitive layer changes with the system dew point value and changed
Tendency chart.As shown in figure 3, the frequency of the QCM humidity sensor is increased with the reduction of dew point.When dew point is (right down to -80.7 DEG C
Should be in 0.5ppm moisture content) when, which still has signal response.
Fig. 4 is that the frequency of the QCM humidity sensor with MOF-801P humidity sensitive layer changes with the system dew point value and changed
Tendency chart.As shown in figure 4, the frequency of the QCM humidity sensor is increased with the reduction of dew point.When dew point is down to -77.2 DEG C
When (corresponding to 0.8ppm moisture content), which still has signal response.
Use above specific example is expounded the present invention, is merely used to help understand the present invention, not to
The limitation present invention.The design of those skilled in the art according to the present invention can also be made and several simply push away
It drills, deform or replaces.These are deduced, deformation or alternative are also fallen into scope of the presently claimed invention.
Claims (10)
1. a kind of quartz crystal microbalance, the quartz crystal microbalance includes quartz crystal matrix, electrode and humidity sensitive layer, described
Electrode is arranged at least part of the quartz crystal matrix, and at least part of the electrode is arranged in the humidity sensitive layer
On, which is characterized in that the humidity sensitive layer includes metal-organic framework material.
2. quartz crystal microbalance according to claim 1, which is characterized in that the metal-organic framework material is Cu-
The combination of one or more of BTC, Fe-BTC, MOF-801 and MOF-801P.
3. quartz crystal microbalance according to claim 2, which is characterized in that the humidity sensitive layer is by the electrode
At least part on coat the metal-organic framework material and be arranged at least part of the electrode.
4. quartz crystal microbalance according to claim 2, which is characterized in that the humidity sensitive layer is by the electrode
At least part on growth in situ Cu-BTC or Fe-BTC and make Cu-BTC or Fe-BTC that the electrode is set extremely
In few a part.
5. quartz crystal microbalance according to claim 1, which is characterized in that the quartz crystal matrix includes two phases
Pair surface, be provided with an electrode on each quartz crystal matrix surface, one layer of humidity sensitive layer be provided on each electrode, it is described
Humidity sensitive layer includes the combination of one or more of Cu-BTC, Fe-BTC, MOF-801 and MOF-801P.
6. quartz crystal microbalance according to claim 5, which is characterized in that each electrode draws a lead,
The lead is electrically connected with electrode formation.
7. quartz crystal microbalance according to claim 6, which is characterized in that the quartz crystal microbalance further includes base
Seat, the lead are fixedly connected with the pedestal and the quartz crystal matrix and the electrode are made to be fixedly supported on the pedestal
On.
8. quartz crystal microbalance according to claim 7, which is characterized in that the quartz crystal microbalance further includes outer
Shell, the quartz crystal matrix and the electrode that the shell accommodates the pedestal and is fixedly supported on the pedestal.
9. a kind of quartz crystal microbalance humidity sensor, which is characterized in that the humidity sensor includes according to claim
Quartz crystal microbalance described in any one of 1-8 and signal acquisition circuit and signal processor.
10. quartz crystal microbalance humidity sensor according to claim 9, which is characterized in that the signal acquisition electricity
Road is common oscillating circuit.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111307886A (en) * | 2020-03-06 | 2020-06-19 | 西南交通大学 | Digital frequency type humidity sensor |
| CN112557356A (en) * | 2020-11-16 | 2021-03-26 | 盐城工学院 | Dual-mode dangerous chemical detection sensor |
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|---|---|---|---|---|
| CN111307886A (en) * | 2020-03-06 | 2020-06-19 | 西南交通大学 | Digital frequency type humidity sensor |
| CN112557356A (en) * | 2020-11-16 | 2021-03-26 | 盐城工学院 | Dual-mode dangerous chemical detection sensor |
| CN114397361A (en) * | 2021-02-23 | 2022-04-26 | 北京理工大学 | Preparation method of green high polymer material for humidity sensor |
| CN114397361B (en) * | 2021-02-23 | 2024-05-24 | 北京理工大学 | Preparation method of green polymer material for humidity sensor |
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