CN106323797A - Graphene oxide modified quartz crystal microbalance sensor for detecting formaldehyde gas, and preparation method and application thereof - Google Patents
Graphene oxide modified quartz crystal microbalance sensor for detecting formaldehyde gas, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a graphene oxide modified quartz crystal microbalance sensor for detecting formaldehyde gas, and a preparation method and an application thereof. The quartz crystal microbalance sensor is obtained by modifying surfaces of an electrode of a quartz crystal microbalance crystal oscillator with a graphene oxide material. The graphene oxide material (GO) is adopted for respectively modifying two surfaces of the electrode of the quartz crystal microbalance crystal oscillator to obtain a graphene oxide modified quartz crystal microbalance crystal oscillator, and thus the quartz crystal microbalance sensor having a response signal on formaldehyde is obtained. The sensor has the sensitive response signal on the formaldehyde gas, and has a good linear response relationship to formaldehyde gas with different concentrations; and within 1 minute, the relatively response signal is obtained, and formaldehyde can be rapidly detected.
Description
Technical field
The present invention relates to gas sensing techniques field.More particularly, to a kind of oxygen detecting formaldehyde gas
The quartz crystal microbalance sensor that functionalized graphene is modified.
Background technology
For living in the most people in modern city, every day the most about more than 80% time
Between spend in indoor.Therefore, IAQ (indoor air quality) just seems more closely more with the relation of health
Important.Although the concentration of indoor polluted gas is the most relatively low, but owing to time of contact is the longest, therefore its accumulation
Exposure is the highest.Weak crowd, the Abwehrkraft des Koepers work relatively low, outdoor such as the oldest, young, sick, residual
Motivation can be less, and the quality of IAQ (indoor air quality) is even more important with their relation.In numerous indoor dirts
In dye gas, formaldehyde is a kind of main pollutant (code for indoor environmental pollution control of civil building engineering
GB50325-2010 requires: in indoor air, the maximum permissible concentration of formaldehyde is 0.08mg/m3).First
Aldehyde is very big to harm, is mainly reflected in the following aspects: (1) stimulation, can stimulate skin,
Eyes and respiratory tract, cause the symptoms such as edema, headache；(2) sensitization, cause allergic dermatitis,
Mottle, necrosis, induce bronchial asthma；(3) mutagenic action, anemia of pregnant woman sucks for a long time and may cause tire
Youngster's deformity, even dead, man sucks for a long time and may result in sperm deformity, death；(4) nasopharynx can be caused
Tumor, the malignant disease such as leukemia.Healthy for broad masses of the people, it is necessary in indoor
The concentration of formaldehyde is within safety range, and therefore, the detection in real time of PARA FORMALDEHYDE PRILLS(91,95) is the most particularly important.
QCM (Quartz Crystal Microbalance, QCM) is that one is with mass change
The sensor of foundation, have that specificity is good, highly sensitive, with low cost and simple operation and other advantages (Ko,
W.；Jung,N.；Lee,M.；Yun,M.；Jeon,S.,ACS Nano 2013,7(8),6685-6690).Gas
, there is a Sauerbrey equation between piezoelectric crystal surface institute's load quality and resonance frequency shift, i.e. in Xiang Zhong
Δ F=-2.26 × 10-6F0 2The frequency change of Δ M/A, wherein Δ F: piezoquartz；F0: piezoquartz
Eigentone (Hz)；The quality (g) of Δ M: piezoelectric crystal surface load material；A: contact area (cm2)。
Thus equation understands, when will optionally detect certain gas componant, first on quarts crystal electrode surface
Modify one layer and there is specific sensitive material, be subsequently placed among the test environment containing gas to be measured, make
Sensitive membrane interacts with gas componant to be measured, the change of quartz crystal vibration frequency just can detect and treat
Survey gas.It can thus be seen that specificity sensitive material has extremely important effect to sensor.Stone
Since ink alkene material self-discovery, with the physicochemical properties of its uniqueness, huge specific surface area, cause
Worldwide extensive concern.Wherein graphene oxide (Graphene Oxide, GO) is on surface and limit
Substantial amounts of carboxyl, hydroxyl and epoxy isoreactivity group is had on edge, can be as the sensitivity of a kind of function admirable
Materials application is on sensor.
Summary of the invention
It is an object of the present invention to provide the quartz that a kind of graphene oxide detecting formaldehyde gas is modified
Crystal microbalance sensor.
Second object of the present invention is the stone providing a kind of graphene oxide detecting formaldehyde gas to modify
The preparation method of English crystal microbalance sensor.
Third object of the present invention is the stone providing a kind of graphene oxide detecting formaldehyde gas to modify
The application of English crystal microbalance sensor.
The instrument of existing detection formaldehyde gas, mainly uses electrochemical principle, detection time typically to use
30 minutes, the detection time was relatively long.The present invention selects selective oxidation grapheme material to detect formaldehyde gas,
Owing to graphene oxide composite material has big specific surface area, surface and edge have substantial amounts of carboxyl,
Hydroxyl and epoxy isoreactivity group, can form intermolecular hydrogen bonding with formaldehyde molecule；Again by itself and quartz-crystal
The micro-balance of body combines, described sensor PARA FORMALDEHYDE PRILLS(91,95) gas, within 1 minute, i.e. has bigger response
Signal, can realize quickly detection with PARA FORMALDEHYDE PRILLS(91,95).
The PARA FORMALDEHYDE PRILLS(91,95) gas of the present invention has the QCM that the graphene oxide of response signal is modified
(QCM) sensor is primarily directed to the silver electrode of QCM crystal oscillator and is processed.The present invention passes through
Hummers method (Hummers, W.S.；Offeman,R.E.,J.Am.Chem.Soc.1958,80(6),
1339-1339) prepare graphene oxide powder, then the graphene oxide powder obtained is scattered in pure
After forming suspension in water, the method for employing drop coating modifies the surface of the silver electrode of QCM crystal oscillator, thus
Obtain the quartz crystal microbalance sensor for detecting formaldehyde gas；Obtained QCM crystal oscillator is placed in gas
To detect the formaldehyde gas of low concentration in body sensing chamber, there is good sensitivity and quickly response.
For reaching above-mentioned first purpose, the present invention uses following technical proposals:
The quartz crystal microbalance sensor that a kind of graphene oxide detecting formaldehyde gas is modified, described stone
English crystal microbalance sensor is to have graphene oxide at the electrode face finish of QCM crystal oscillator
Material.
Preferably, the electrode of described QCM crystal oscillator is silver electrode.
Preferably, two surfaces of described electrode are all modified with graphene oxide composite material, repairing of two surfaces
Decorations amount is 3.5～12.5 micrograms.
Preferably, the electrode area of described QCM crystal oscillator is 0.126～0.283 square centimeter.
It is highly preferred that described electrode area is 0.196 square centimeter.
Preferably, described graphene oxide composite material is to be prepared by Hummers method.
For reaching above-mentioned second purpose, the present invention uses following technical proposals:
The QCM sensing that the graphene oxide of a kind of detection formaldehyde gas as above is modified
The preparation method of device, comprises the steps:
1) take 5～15 milligrams of graphene oxide composite material to be scattered in the pure water of 4～6 milliliters, ultrasonic disperse shape
Become homogeneous scattered suspension；
2) 4～8 microlitre steps 1 are taken) the homogeneous scattered suspension that obtains, drop coating is in the micro-sky of quartz crystal
Electrode one side surface that optical flat shakes；
3) by step 2) the QCM crystal oscillator that obtains inserts in drying baker and is dried, then take
4～8 microlitre steps 1) the homogeneous scattered suspension of gained, drop coating is in the electrode of QCM crystal oscillator
Opposite side surface；
4) by step 3) the QCM crystal oscillator that obtains inserts in drying baker and is dried, to obtain final product
Two surfaces to the electrode at QCM crystal oscillator are all modified with the quartz of graphene oxide composite material
Crystal microbalance sensor.
Preferably, step 1) in, the time of ultrasonic disperse is 20～30 minutes.
Preferably, step 3) in, the temperature being dried is 50～70 degrees Celsius, and drying time is 1～2 hour.
Preferably, step 4) in, the temperature being dried is 50～70 degrees Celsius, and drying time is 10～15
Hour.
Preferably, described pure water be resistivity be the ultra-pure water of 15～18.2M Ω cm.
It is highly preferred that described pure water is resistivity is the ultra-pure water of 18.2M Ω cm.
The PARA FORMALDEHYDE PRILLS(91,95) gas of the present invention has the QCM that the graphene oxide of response signal is modified
Sensor, is to use graphene oxide composite material, carries out two surfaces of the silver electrode of QCM crystal oscillator respectively
Modify, obtain the QCM crystal oscillator that graphene oxide is modified, thus obtain PARA FORMALDEHYDE PRILLS(91,95) gas and have response signal
Graphene oxide modify quartz crystal microbalance sensor,
For reaching above-mentioned 3rd purpose, the present invention discloses the oxygen of a kind of detection formaldehyde gas as above
The quartz crystal microbalance sensor that functionalized graphene is modified application in detection formaldehyde gas.
Preferably, described application includes following detecting step:
1) by described quartz crystal microbalance sensor, it is placed in the gas in QCM detecting system
In body sensing chamber, then in gas detection cell, flow with 400mL/min is passed through air, passes through simultaneously
The computer being furnished with signal acquiring system records by the QCM crystal oscillator sensing in gas detection cell
, the response signal of the frequency that the change of the frequency of vibration of the silver electrode gathered by cymometer produces；
2) to step 1) described in gas detection cell in be passed through variable concentrations with the flow of 400mL/min
Formaldehyde gas, records by the quartz in gas detection cell by being furnished with the computer of signal acquiring system simultaneously
The frequency that the frequency of vibration change of silver electrode that crystal microbalance crystal oscillator senses, that gathered by cymometer produces
Response signal；
3) arrange step 2) the frequency of vibration changing value of silver electrode of QCM crystal oscillator, point
Analysis comparison step 1) and step 2) in QCM crystal oscillator silver electrode frequency of vibration change.
Specifically, the PARA FORMALDEHYDE PRILLS(91,95) gas of the present invention has the quartz-crystal that the graphene oxide of response signal is modified
Body micro-balance (QCM) sensor (crystal oscillator), in the detection method of the formaldehyde gas for detecting low concentration
One of be:
1) by the quartz crystal microbalance sensor of the present invention, it is placed in QCM (QCM)
In gas detection cell in detecting system, then in gas detection cell, flow with 400mL/min is passed through
Air, records by the quartz crystal in gas detection cell by being furnished with the computer of signal acquiring system simultaneously
The frequency of vibration change of silver electrode that micro-balance (QCM) crystal oscillator senses, that gathered by cymometer produces
The response signal of frequency；
2) in the gas detection cell of step (1), flow with 400mL/min is passed through concentration as 1.7ppm
Formaldehyde gas, record by the stone in gas detection cell by being furnished with the computer of signal acquiring system simultaneously
The frequency of vibration change of silver electrode that English crystal microbalance (QCM) crystal oscillator senses, that gathered by cymometer
The response signal of the frequency produced；
3) the frequency of vibration changing value of the silver electrode of the QCM crystal oscillator of step (2) is arranged,
The frequency of vibration of the silver electrode of the QCM crystal oscillator of com-parison and analysis step (1) and step (2)
Change, by frequency signal response curve, it can be seen that the micro-sky of quartz crystal that this graphene oxide is modified
Flat (QCM) sensor PARA FORMALDEHYDE PRILLS(91,95) gas has good response signal.
Specifically, the PARA FORMALDEHYDE PRILLS(91,95) gas of the present invention has the quartz-crystal that the graphene oxide of response signal is modified
Body micro-balance (QCM) sensor (crystal oscillator), in the detection method of the formaldehyde gas for detecting low concentration
Two:
1) by the quartz crystal microbalance sensor of the present invention, it is placed in QCM (QCM)
In gas detection cell in detecting system, then in gas detection cell, flow with 400mL/min is passed through
Air, records by the quartz crystal in gas detection cell by being furnished with the computer of signal acquiring system simultaneously
The frequency of vibration change of silver electrode that micro-balance (QCM) crystal oscillator senses, that gathered by cymometer produces
The response signal of frequency；
2) in the gas detection cell of step (1), flow with 400mL/min each leads into variable concentrations
Formaldehyde gas (concentration of formaldehyde gas is respectively as follows: 3.5ppm；2.6ppm；1.7ppm；0.9ppm；
0.5ppm), record by the quartz-crystal in gas detection cell by being furnished with the computer of signal acquiring system simultaneously
The frequency of vibration change of silver electrode that body micro-balance (QCM) crystal oscillator senses, that gathered by cymometer produces
The response signal of frequency；
3) the frequency of vibration changing value of the silver electrode of the QCM crystal oscillator of step (2) is arranged,
The frequency of vibration of the silver electrode of the QCM crystal oscillator of com-parison and analysis step (1) and step (2)
Change, by frequency signal response curve, it can be seen that the micro-sky of quartz crystal that this graphene oxide is modified
Flat (QCM) sensor has good linear response signal to the formaldehyde gas of variable concentrations.
QCM detecting system of the present invention is by air distribution system, qcm sensor detecting system and letter
Number acquisition system three part composition.Air distribution system uses saturated vapor diffusion method preparation low concentration formaldehyde gas,
Politef and stainless steel material is all have employed, to reduce absorption and the corruption to system in all gas circuits
Erosion, using air as carrier gas, and by the flow velocity of three groups of flow controllers control gases, gas detection cell is put
In calorstat, to ensure stablizing of formaldehyde gas concentration.After the concentration of formaldehyde gas to be prepared is stable,
By cross valve, formaldehyde gas is sent in gas detection cell, gas and the graphene oxide of sensor surface
Sensitive membrane is had an effect and causes the change of frequency, by signal acquiring system record, analytical data.Pass through
Experiment, QCM (QCM) the sensor PARA FORMALDEHYDE PRILLS(91,95) gas that graphene oxide is modified has sound
Induction signal, meanwhile, the quartz crystal microbalance sensor that graphene oxide the is modified formaldehyde to variable concentrations
Gas has good linear response relationship.
Beneficial effects of the present invention is as follows:
The PARA FORMALDEHYDE PRILLS(91,95) gas of the present invention has the QCM that the graphene oxide of response signal is modified
Sensor, is to use graphene oxide composite material, carries out two surfaces of the silver electrode of QCM crystal oscillator respectively
Modify, obtain the QCM crystal oscillator that graphene oxide is modified, thus obtain PARA FORMALDEHYDE PRILLS(91,95) gas and have response signal
Graphene oxide modify quartz crystal microbalance sensor.Described sensor PARA FORMALDEHYDE PRILLS(91,95) gas has spirit
Quick response signal, has good linear response relationship to the formaldehyde gas of variable concentrations；And at 1 point
Within clock, i.e. there is bigger response signal, quickly detection can be realized with PARA FORMALDEHYDE PRILLS(91,95).
Accompanying drawing explanation
Below in conjunction with the accompanying drawings the detailed description of the invention of the present invention is described in further detail.
Fig. 1 illustrates the transmission electron microscope of the graphene oxide that the embodiment of the present invention 1 uses Hummers method to prepare
Photo.
Fig. 2 illustrates the QCM sensing that graphene oxide prepared by the embodiment of the present invention 2 is modified
The device response curve to the formaldehyde gas of 1.7ppm.
Fig. 3 illustrates the QCM sensing that graphene oxide prepared by the embodiment of the present invention 2 is modified
The device three round robin curves to the formaldehyde gas of 1.7ppm.
Fig. 4 illustrates the QCM sensing that graphene oxide prepared by the embodiment of the present invention 2 is modified
The device response curve to variable concentrations formaldehyde gas.
Fig. 5 illustrates the QCM sensing that graphene oxide prepared by the embodiment of the present invention 2 is modified
Linearity curve between frequency response values and the concentration of formaldehyde of device.
Detailed description of the invention
In order to be illustrated more clearly that the present invention, below in conjunction with preferred embodiments and drawings, the present invention is done into one
The explanation of step.Parts similar in accompanying drawing are indicated with identical reference.Those skilled in the art
Should be appreciated that following specifically described content is illustrative and be not restrictive, should not limit with this
Protection scope of the present invention.
Embodiment 1
The quartz crystal microbalance sensor that a kind of graphene oxide detecting formaldehyde gas is modified, at quartz
The silver electrode both side surface of crystal microbalance crystal oscillator is modified with graphene oxide composite material, described silver electrode area
Being 0.196 square centimeter, the modification amount on two surfaces is 3.5～5 micrograms.
The preparation method of described sensor is as follows:
(1) at room temperature take 5～7 milligrams of graphene oxide composite material using Hummers method to prepare to be scattered in
In the pure water (resistivity 18.2M Ω cm) of 4～6 milliliters, ultrasonic disperse 20～form homogeneous dispersion in 30 minutes
Suspension；
(2) the homogeneous scattered suspension that 4～8 microlitre steps (1) obtain, drop coating are taken with microsyringe
(the area of the silver electrode of this QCM crystal oscillator on a side surface in the two sides of the silver electrode of QCM crystal oscillator
It is 0.196cm2)；
(3) the QCM crystal oscillator that step (2) obtains is inserted in drying baker, do under the conditions of 60 DEG C
Dry 1～2 hour, then pipette the 4～8 homogeneous scattered suspensions of microlitre step (1) gained with microsyringe,
Drop coating is on the opposite side surface of the silver electrode of QCM crystal oscillator；
(4) the QCM crystal oscillator that step (3) obtains is inserted in drying baker, do under the conditions of 60 DEG C
Dry 10～15 hours, obtain all modifying aerobic on two surfaces of the silver electrode of QCM crystal oscillator
The quartz crystal microbalance sensor of functionalized graphene, wherein: the modification amount on two surfaces is all 3.5～5 micrograms.
Embodiment 2
The quartz crystal microbalance sensor that a kind of graphene oxide detecting formaldehyde gas is modified, at quartz
The silver electrode both side surface of crystal microbalance crystal oscillator is modified with graphene oxide composite material, described silver electrode area
Being 0.196 square centimeter, the modification amount on two surfaces is 5～6.5 micrograms.
The preparation method of described sensor is as follows:
(1) at room temperature take 7～9 milligrams of graphene oxide composite material using Hummers method to prepare to be scattered in
In the pure water (resistivity 18.2M Ω cm) of 4～6 milliliters, ultrasonic disperse 20～form homogeneous dispersion in 30 minutes
Suspension；
(2) the homogeneous scattered suspension that 4～8 microlitre steps (1) obtain, drop coating are taken with microsyringe
(the area of the silver electrode of this QCM crystal oscillator on a side surface in the two sides of the silver electrode of QCM crystal oscillator
It is 0.196cm2)；
(3) the QCM crystal oscillator that step (2) obtains is inserted in drying baker, do under the conditions of 60 DEG C
Dry 1～2 hour, then pipette the 4～8 homogeneous scattered suspensions of microlitre step (1) gained with microsyringe,
Drop coating is on the opposite side surface of the silver electrode of QCM crystal oscillator；
(4) the QCM crystal oscillator that step (3) obtains is inserted in drying baker, do under the conditions of 60 DEG C
Dry 10～15 hours, obtain all modifying aerobic on two surfaces of the silver electrode of QCM crystal oscillator
The quartz crystal microbalance sensor of functionalized graphene, wherein: the modification amount on two surfaces is all 5～6.5 micrograms.
Inventive sensor is applied to detect the formaldehyde gas of fixed concentration, and step is as follows:
(1) qcm sensor that embodiment 2 is obtained, the gas detecting being placed in the detecting system of QCM
In room, then in gas detection cell, flow with 400mL/min is passed through air, simultaneously by being furnished with letter
The computer of number acquisition system record that sensed by the QCM crystal oscillator in gas detection cell, gathered by cymometer
The response signal of frequency that produces of the frequency of vibration change of silver electrode；
(2) in the gas detection cell of step (1), flow with 400mL/min is passed through concentration as 1.7ppm
Formaldehyde gas, record by gas detection cell by being furnished with the computer of signal acquiring system simultaneously
The response of the frequency that the frequency of vibration change of silver electrode that QCM crystal oscillator senses, that gathered by cymometer produces
Signal；
(4) the frequency of vibration changing value of the silver electrode of the QCM crystal oscillator of step (1) and step (2) is arranged,
The frequency of vibration change of the silver electrode of the QCM crystal oscillator of com-parison and analysis step (1) and step (2), shows
The qcm sensor that this graphene oxide is modified has response signal to the formaldehyde gas of 1.7ppm.
To the testing result of the formaldehyde gas of 1.7ppm as shown in fig. 2, it can be seen that when formaldehyde gas enters
Entering after sensing chamber, the frequency of QCM crystal oscillator declines immediately, and when 60 seconds, frequency change can reach 37
Hz, after frequency signal is stable, frequency change can reach about 55Hz.When purging sensing chamber with air
Time, frequency signal is recovered substantially.
To three cycle detection results of the formaldehyde gas of 1.7ppm fig. 3, it is shown that oxidation
The quartz crystal microbalance sensor of graphene modified is in signal response magnitude, response time and recovery time
Aspect is the most preferably repeated, it was demonstrated that the quartz crystal microbalance sensor pair that this graphene oxide is modified
Formaldehyde gas has preferable repeatability, can reuse.
Inventive sensor is applied to detect the formaldehyde gas of variable concentrations, and step is as follows:
(1) qcm sensor that embodiment 2 is obtained, the gas detecting being placed in the detecting system of QCM
In room, then in gas detection cell, flow with 400mL/min is passed through air, simultaneously by being furnished with letter
The computer of number acquisition system record that sensed by the QCM crystal oscillator in gas detection cell, gathered by cymometer
The response signal of frequency that produces of the frequency of vibration change of silver electrode；
(2) in the gas detection cell of step (1), the first of variable concentrations it is passed through with the flow of 400mL/min
(concentration of formaldehyde gas is respectively as follows: 3.5ppm to aldehyde gas；2.6ppm；1.7ppm；0.9ppm；0.5
Ppm), record by the QCM in gas detection cell brilliant by being furnished with the computer of signal acquiring system simultaneously
The response signal of the frequency that the frequency of vibration change of silver electrode that shake sensing, that gathered by cymometer produces；
(4) the frequency of vibration changing value of the silver electrode of the QCM crystal oscillator of step (1) and step (2) is arranged,
The frequency of vibration change of the silver electrode of the QCM crystal oscillator of com-parison and analysis step (1) and step (2), shows
The qcm sensor that this graphene oxide is modified all has response signal to the formaldehyde gas of variable concentrations；
To the testing result of the formaldehyde gas of variable concentrations as shown in Figure 4, it can be seen that this graphite oxide
The formaldehyde gas of variable concentrations is all had signal to respond by the quartz crystal microbalance sensor that alkene is modified, and
And along with the reduction of concentration of formaldehyde, frequency response signal value is also proportionally reduced.
Between frequency response values and the concentration of formaldehyde of the quartz crystal microbalance sensor that graphene oxide is modified
Relation as it is shown in figure 5, frequency response signal value and concentration of formaldehyde have linear response curve, accordingly
Linear equation is as follows: Δ F=-16.9c-6.6, r=0.96, and wherein Δ F is the frequency change of piezoquartz；c
It it is concentration of formaldehyde；R is the goodness of fit.
Embodiment 3
The quartz crystal microbalance sensor that a kind of graphene oxide detecting formaldehyde gas is modified, at quartz
The silver electrode both side surface of crystal microbalance crystal oscillator is modified with graphene oxide composite material, described silver electrode area
Being 0.126 square centimeter, the modification amount on two surfaces is 6.5～8 micrograms.
The preparation method of described sensor is as follows:
(1) at room temperature take 9～11 milligrams of graphene oxide composite material using Hummers method to prepare to be scattered in
In the pure water (resistivity 18.2M Ω cm) of 4～6 milliliters, ultrasonic disperse 20～form homogeneous dispersion in 30 minutes
Suspension；
(2) the homogeneous scattered suspension that 4～8 microlitre steps (1) obtain, drop coating are taken with microsyringe
(the area of the silver electrode of this QCM crystal oscillator on a side surface in the two sides of the silver electrode of QCM crystal oscillator
It is 0.196cm2)；
(3) the QCM crystal oscillator that step (2) obtains is inserted in drying baker, do under the conditions of 50 DEG C
Dry 1～2 hour, then pipette the 4～8 homogeneous scattered suspensions of microlitre step (1) gained with microsyringe,
Drop coating is on the opposite side surface of the silver electrode of QCM crystal oscillator；
(4) the QCM crystal oscillator that step (3) obtains is inserted in drying baker, do under the conditions of 50 DEG C
Dry 10～15 hours, obtain all modifying aerobic on two surfaces of the silver electrode of QCM crystal oscillator
The quartz crystal microbalance sensor of functionalized graphene, wherein: the modification amount on two surfaces is all 6.5～8 micrograms.
Detection results in described sensor PARA FORMALDEHYDE PRILLS(91,95) gas is similar to Example 2.
Embodiment 4
The quartz crystal microbalance sensor that a kind of graphene oxide detecting formaldehyde gas is modified, at quartz
The silver electrode both side surface of crystal microbalance crystal oscillator is modified with graphene oxide composite material, described silver electrode area
Being 0.236 square centimeter, the modification amount on two surfaces is 8～9.5 micrograms.
The preparation method of described sensor is as follows:
(1) 11～13 milligrams of graphene oxide composite material dispersions using Hummers method to prepare at room temperature are taken
In the pure water of 4～6 milliliters (resistivity 18.2M Ω cm), ultrasonic disperse 20～formation in 30 minutes are homogeneous
Scattered suspension；
(2) the homogeneous scattered suspension that 4～8 microlitre steps (1) obtain, drop coating are taken with microsyringe
(the area of the silver electrode of this QCM crystal oscillator on a side surface in the two sides of the silver electrode of QCM crystal oscillator
It is 0.196cm2)；
(3) the QCM crystal oscillator that step (2) obtains is inserted in drying baker, do under the conditions of 70 DEG C
Dry 1～2 hour, then pipette the 4～8 homogeneous scattered suspensions of microlitre step (1) gained with microsyringe,
Drop coating is on the opposite side surface of the silver electrode of QCM crystal oscillator；
(4) the QCM crystal oscillator that step (3) obtains is inserted in drying baker, do under the conditions of 70 DEG C
Dry 10～15 hours, obtain all modifying aerobic on two surfaces of the silver electrode of QCM crystal oscillator
The quartz crystal microbalance sensor of functionalized graphene, wherein: the modification amount on two surfaces is all 8～9.5 micrograms.
Detection results in described sensor PARA FORMALDEHYDE PRILLS(91,95) gas is similar to Example 2.
Embodiment 5
The quartz crystal microbalance sensor that a kind of graphene oxide detecting formaldehyde gas is modified, at quartz
The silver electrode both side surface of crystal microbalance crystal oscillator is modified with graphene oxide composite material, described silver electrode area
Being 0.283 square centimeter, the modification amount on two surfaces is 9.5～11 micrograms.
The preparation method of described sensor is as follows:
(1) 13～15 milligrams of graphene oxide composite material dispersions using Hummers method to prepare at room temperature are taken
In the pure water of 4～6 milliliters (resistivity 18.2M Ω cm), ultrasonic disperse 20～formation in 30 minutes are homogeneous
Scattered suspension；
(2) the homogeneous scattered suspension that 4～8 microlitre steps (1) obtain, drop coating are taken with microsyringe
(the area of the silver electrode of this QCM crystal oscillator on a side surface in the two sides of the silver electrode of QCM crystal oscillator
It is 0.196cm2)；
(3) the QCM crystal oscillator that step (2) obtains is inserted in drying baker, do under the conditions of 60 DEG C
Dry 1～2 hour, then pipette the 4～8 homogeneous scattered suspensions of microlitre step (1) gained with microsyringe,
Drop coating is on the opposite side surface of the silver electrode of QCM crystal oscillator；
(4) the QCM crystal oscillator that step (3) obtains is inserted in drying baker, do under the conditions of 60 DEG C
Dry 10～15 hours, obtain all modifying aerobic on two surfaces of the silver electrode of QCM crystal oscillator
The quartz crystal microbalance sensor of functionalized graphene, wherein: the modification amount on two surfaces is all 9.5～11 micro-
Gram.
Detection results in described sensor PARA FORMALDEHYDE PRILLS(91,95) gas is similar to Example 2.
Obviously, the above embodiment of the present invention is only for clearly demonstrating example of the present invention, and
It is not the restriction to embodiments of the present invention, for those of ordinary skill in the field,
Can also make other changes in different forms on the basis of described above, here cannot be to all
Embodiment give exhaustive, every belong to the obvious change that technical scheme extended out
Change or change the row still in protection scope of the present invention.
Claims (10)
1. detecting the quartz crystal microbalance sensor that the graphene oxide of formaldehyde gas is modified, it is special
Levy and be: described quartz crystal microbalance sensor is to repair at the electrode surface of QCM crystal oscillator
It is decorated with graphene oxide composite material.
The quartz-crystal that a kind of graphene oxide detecting formaldehyde gas the most according to claim 1 is modified
Body microbalance sensor, it is characterised in that: the electrode of described QCM crystal oscillator is silver electrode.
The quartz-crystal that a kind of graphene oxide detecting formaldehyde gas the most according to claim 1 is modified
Body microbalance sensor, it is characterised in that: two surfaces of described electrode are all modified with graphene oxide material
Material, the modification amount on two surfaces is 3.5～12.5 micrograms.
The quartz-crystal that a kind of graphene oxide detecting formaldehyde gas the most according to claim 1 is modified
Body microbalance sensor, it is characterised in that: the electrode area of described QCM crystal oscillator is
0.126～0.283 square centimeter；Preferably, described electrode area is 0.196 square centimeter.
The quartz-crystal that a kind of graphene oxide detecting formaldehyde gas the most according to claim 1 is modified
Body microbalance sensor, it is characterised in that: described graphene oxide composite material is to be prepared into by Hummers method
Arrive.
6. the stone that the graphene oxide of the detection formaldehyde gas as described in Claims 1 to 5 is arbitrary is modified
The preparation method of English crystal microbalance sensor, it is characterised in that comprise the steps:
1) take 5～15 milligrams of graphene oxide composite material to be scattered in the pure water of 4～6 milliliters, ultrasonic disperse shape
Become homogeneous scattered suspension；
2) 4～8 microlitre steps 1 are taken) the homogeneous scattered suspension that obtains, drop coating is in the micro-sky of quartz crystal
Electrode one side surface that optical flat shakes；
3) by step 2) the QCM crystal oscillator that obtains inserts in drying baker and is dried, then take
4～8 microlitre steps 1) the homogeneous scattered suspension of gained, drop coating is in the electrode of QCM crystal oscillator
Opposite side surface；
4) by step 3) the QCM crystal oscillator that obtains inserts in drying baker and is dried, to obtain final product
Two surfaces to the electrode at QCM crystal oscillator are all modified with the quartz of graphene oxide composite material
Crystal microbalance sensor.
The quartz-crystal that a kind of graphene oxide detecting formaldehyde gas the most according to claim 6 is modified
The preparation method of body microbalance sensor, it is characterised in that: step 1) in, the time of ultrasonic disperse is
20～30 minutes；Step 3) in, the temperature being dried is 50～70 degrees Celsius, and drying time is 1～2 hour；
Step 4) in, the temperature being dried is 50～70 degrees Celsius, and drying time is 10～15 hours.
The quartz-crystal that a kind of graphene oxide detecting formaldehyde gas the most according to claim 6 is modified
The preparation method of body microbalance sensor, it is characterised in that: described pure water be resistivity be 15～18.2
The ultra-pure water of M Ω cm；Preferably, described pure water be resistivity be the ultra-pure water of 18.2M Ω cm.
9. the stone that the graphene oxide of the detection formaldehyde gas as described in Claims 1 to 5 is arbitrary is modified
The application in detection formaldehyde gas of the English crystal microbalance sensor.
The quartz that a kind of graphene oxide detecting formaldehyde gas the most according to claim 9 is modified
The application of crystal microbalance sensor, it is characterised in that include following detecting step:
1) by described quartz crystal microbalance sensor, it is placed in the gas in QCM detecting system
In body sensing chamber, then in gas detection cell, flow with 400mL/min is passed through air, passes through simultaneously
The computer being furnished with signal acquiring system records by the QCM crystal oscillator sensing in gas detection cell
, the response signal of the frequency that the change of the frequency of vibration of the silver electrode gathered by cymometer produces；
2) to step 1) described in gas detection cell in be passed through variable concentrations with the flow of 400mL/min
Formaldehyde gas, records by the quartz in gas detection cell by being furnished with the computer of signal acquiring system simultaneously
The frequency that the frequency of vibration change of silver electrode that crystal microbalance crystal oscillator senses, that gathered by cymometer produces
Response signal；
3) arrange step 2) the frequency of vibration changing value of silver electrode of QCM crystal oscillator, point
Analysis comparison step 1) and step 2) in QCM crystal oscillator silver electrode frequency of vibration change.
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