CN104048893B - For detecting the quartz crystal microbalance sensor of HCN gas and preparation method thereof and application - Google Patents
For detecting the quartz crystal microbalance sensor of HCN gas and preparation method thereof and application Download PDFInfo
- Publication number
- CN104048893B CN104048893B CN201410276034.3A CN201410276034A CN104048893B CN 104048893 B CN104048893 B CN 104048893B CN 201410276034 A CN201410276034 A CN 201410276034A CN 104048893 B CN104048893 B CN 104048893B
- Authority
- CN
- China
- Prior art keywords
- electrode
- qcm
- hcn gas
- nickel hydroxide
- crystal oscillator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The present invention relates to can be used for quartz crystal microbalance sensor quickly detecting severe toxicity HCN gas and its preparation method and application.The quartz crystal microbalance sensor of the present invention, is two surfaces of the electrode of QCM crystal oscillator at quartz crystal microbalance sensor nickel hydroxide balls of being all modified with the micron order flower-like structure of a diameter of 3～6 μm.It is little that the quartz crystal microbalance sensor of the present invention has volume, can conveniently be transferred to the advantage in HCN gas-detecting device.Use the electrode of the QCM crystal oscillator of the nickel hydroxide ball modification of micron order flower-like structure, electrode as quartz crystal microbalance sensor, this quartz crystal microbalance sensor is sensitive to the response of HCN gas, and the HCN gas for low concentration (20ppm) shows good response.
Description
Technical field
The invention belongs to the sensing detection category to severe toxicity gas HCN etc., particularly to can be used for quickly examining
Survey quartz crystal microbalance sensor of severe toxicity HCN gas and its preparation method and application.
Background technology
Blausure (German) is a kind of colourless hypertoxic gas with Semen Armeniacae Amarum taste, and chemical formula is HCN, and it divides relatively
Son amount is 27.03, and relative density is 0.69, and fusing point is-14 DEG C, and boiling point is 26 DEG C.HCN is a kind of severe toxicity
Gas, was once used as chemical weapons, belonged to blood borne chemical warfare agent, Main Function: limit blood absorbs
Oxygen, reaches the purpose making people's anoxia lethal.The toxicity of HCN gas is about 30 times of CO gas, when
People be exposed to lower 1 minute of HCN gas that concentration is 300ppm just can causing death (Osi ska, M.,
Reaction Kinetics,Mechanisms and Catalysis,2013.109(1):p.57-65.).Therefore,
Develop the method for quick to HCN gas and become particularly important.Detect HCN gas the most in the world
Universal method is .gamma.-pyridinecarboxylic acid-pyrazolone method, and the method has that detection limit is low, highly sensitive, it is reliable to analyze
Feature, but operation is the most complicated, is not suitable for the quick detection to HCN gas.Other method such as electrification
Method, atomic absorption spectrophotometry are also not suitable for the quick inspection of HCN gas because of the restriction of himself
Survey.
QCM is a kind of high sensor with mass change as foundation, has ultralow
Detection limit and the feature of quickly response.Low additionally, due to its cost, volume is little and the characteristic of superior performance,
The needs of reality application can be met, there is good application prospect.QCM is as sensor
Application relate to procedure below: the 1. synthesis of load sample and preparation.2. gained sample is carried on quartz
The electrode surface of crystal microbalance crystal oscillator, obtains quartz crystal microbalance sensor.3. quartz crystal is micro-
Balance sensor is connected to detection equipment, carries out coherent detection.
Wherein the load capacity of sample is to calculate the important parameter of transducer sensitivity, and load capacity can be by
Sauerbrey equation (Sauerbrey, G., Zeitschrift f ü r Physik, 1959.155 (2): p.206-222.)
Try to achieve: Δ F=-2.26 × 10-6F2ΔM/A
The frequency of vibration changing value of wherein Δ F: QCM crystal oscillator；F: QCM
The original frequency of vibration (Hz) of crystal oscillator；The loaded material of electrode surface of Δ M: QCM crystal oscillator
Quality (g)；A: gas sensing area (cm2)。
When QCM is applied to toxic and harmful detection as sensor, premise be gas with
Have an effect between the sample of load, cause the loaded material of electrode surface of QCM crystal oscillator
Quality change, thus produce response signal, simultaneously can be by the vibration of QCM crystal oscillator
The changing value of frequency derives the concentration of analyte.
Summary of the invention
An object of the present invention is to provide the micro-sky of quartz crystal that can be used for quickly detecting severe toxicity HCN gas
Sensor.
The two of the purpose of the present invention are to provide a kind of quartz crystal that can be used for quickly detecting severe toxicity HCN gas
The preparation method of microbalance sensor.
The three of the purpose of the present invention are to provide the micro-sky of quartz crystal that can be used for quickly detecting severe toxicity HCN gas
Sensor application in terms of the hypertoxic HCN gas of detection low concentration.
The quartz crystal microbalance sensor for quickly detection severe toxicity HCN gas of the present invention, mainly relates to
And the modification of the electrode surface of QCM crystal oscillator.Nanometer is prepared by low-temperature hydrothermal response strategy
The nickel hydroxide ball powder of level flower-like structure, by the nickel hydroxide ball powder of prepared nanoscale flower-like structure
After being dispersed in deionized water formation suspension, by above-mentioned suspension, modified by the method for drop coating
To the electrode surface of QCM crystal oscillator, thus prepare for quickly detection severe toxicity HCN gas
Quartz crystal microbalance sensor；Finally prepared quartz crystal microbalance sensor is placed in severe toxicity gas
Carrying out the quick detection of HCN gas in the sensing chamber of HCN, this quartz crystal microbalance sensor is to play
The detected representation of poison HCN gas has gone out high sensitivity, high selective feature.
The quartz crystal microbalance sensor for quickly detection severe toxicity HCN gas of the present invention, is at stone
Two surfaces of the electrode of the QCM crystal oscillator of English crystal microbalance sensor are all modified with diameter
It is the nickel hydroxide ball of the micron order flower-like structure of 3～6 μm, and each leaf of flower-like structure nickel hydroxide ball
The thickness of sheet is 20～30nm.
Two surfaces of the electrode of described QCM crystal oscillator are all modified with a diameter of 3～6 μm
The nickel hydroxide ball of micron order flower-like structure, the modification amount on two surface is all 6～10 micrograms.
The preparation side for the quickly quartz crystal microbalance sensor of detection severe toxicity HCN gas of the present invention
Method comprises the following steps:
(1) the nickel hydroxide ball of the micron order flower-like structure of a diameter of 3～6 μm of 7～10 milligrams is scattered in
In the deionized water of 5～10 milliliters, process through ultrasonic disperse, form homogeneous scattered suspension；Described
The thickness of each blade of nickel hydroxide ball of flower-like structure be 20～30nm；
(2) 4～8 microlitres (available microsyringe pipettes) the homogeneous scattered suspension of step (1) gained is taken,
Slowly drop coating is in a side surface of the electrode of QCM crystal oscillator；
(3) electrode of the QCM crystal oscillator being loaded with described suspension that step (2) is obtained
Being placed in drying baker, after being dried under room temperature condition, then (available microsyringe moves to take 4～8 microlitres
Take) the homogeneous scattered suspension of step (1) gained, slow drop coating is in the electrode of QCM crystal oscillator
Opposite side surface；
(4) electrode of QCM crystal oscillator step (3) obtained is placed in drying baker, in room temperature
Under the conditions of be dried, all obtain being modified with straight on two surfaces of the electrode of QCM crystal oscillator
Footpath is the nickel hydroxide ball of the micron order flower-like structure of 3～6 μm, and the nickel hydroxide ball of flower-like structure is every
The thickness of one blade is 20～30nm.
The material of the electrode of described QCM crystal oscillator is golden or silver-colored；Described quartz crystal is micro-
The area of the electrode of balance crystal oscillator is 0.196cm2。
Described deionization resistivity of water is 18.2M Ω cm.
The described time being dried is 9～12 hours.
The nickel hydroxide ball of described micron order flower-like structure is prepared by following methods:
(1) take 1～3 gram of nickel nitrate to be dissolved in the deionized water of 20～120 milliliters, be stirred vigorously to being completely dissolved；
(2) ammonia of 3～17 milliliters is joined in the solution of step (1), agitated obtain clear solution；
(3) dodecylbenzene sodium sulfonate taking 0.01～0.8 gram is dissolved in the deionized water of 20～120 milliliters, stirs
Mix to being completely dissolved；
(4) solution that step (3) obtains is poured in the clear solution that step (2) prepares, be stirred vigorously (relatively
The time of good stirring is 6～12 hours) so that it is mix homogeneously；
(5) solution that step (4) obtains is transferred in the stainless steel cauldron with politef as liner,
Seal, keep 6～12 hours under conditions of temperature is 100～170 DEG C, be washed with deionized and obtain
Product, is then dried the product after washing under conditions of temperature is 60～90 DEG C, final
The nickel hydroxide ball powder of jade-green micron order flower-like structure, the hydrogen-oxygen of this micron order flower-like structure are arrived
Change a diameter of 3～6 μm of nickel ball, and the thickness of each blade of the nickel hydroxide ball of flower-like structure is
20～30nm.
Being washed with deionized described in step (5), preferably washing times are 3～7 times.
The concentration of described ammonia is 25wt%.
Described deionization resistivity of water is 18.2M Ω cm.
The quartz crystal microbalance sensor for quickly detection severe toxicity HCN gas of the present invention can be used for examining
Survey the HCN gas of low concentration.
The method of described detection is:
(1) quartz crystal microbalance sensor of the present invention is placed in the sensing chamber of severe toxicity HCN gas, so
After pass to the air of 800mL/min flow, record by detecting by being furnished with the computer of signal acquiring system
The response signal of the frequency that the frequency of vibration change of the electrode of the QCM crystal oscillator in room produces；
(2) quartz crystal microbalance sensor of the present invention is placed in the sensing chamber of severe toxicity HCN gas, so
After to pass to flow be 800mL/min, concentration is the HCN gas of 20ppm, by being furnished with signals collecting system
The computer of system records the frequency of vibration change of the electrode by the QCM crystal oscillator in sensing chamber and produces
The response signal of raw frequency；
(3) vibration of the electrode of the QCM crystal oscillator of com-parison and analysis step (1) and step (2)
Frequency changes, and the frequency of vibration of the electrode of the QCM crystal oscillator of step (2) rises rapidly, and 10
In second, the increase value to the response signal (Δ F) of the frequency of 20ppm HCN gas can reach 624Hz,
Determine the existence of HCN gas.
The quartz crystal microbalance sensor for quickly detection severe toxicity HCN gas of the present invention can also be used
In the detection of the saturated vapor of acetone, ether, water or ethanol etc., the method for its detection is:
(1) by the quartz crystal microbalance sensor of the present invention, it is respectively placed in the sensing chamber of severe toxicity HCN gas
In, pass to the saturated vapor of the acetone of 800mL/min flow, ether, water or ethanol etc. the most respectively,
And the HCN gas that concentration is 20ppm；Record by detecting by being furnished with the computer of signal acquiring system
The response signal of the frequency that the frequency of vibration change of the electrode of the QCM crystal oscillator in room produces；
(2) the frequency of vibration changing value of the electrode of the QCM crystal oscillator of analytical procedure (1), permissible
Find that the electrode of QCM crystal oscillator is to the response signal of the frequency of HCN gas and to acetone, second
The response signal of the frequency of the saturated vapor of ether, water or ethanol etc. is contrary, it is determined that QCM
The electrode of crystal oscillator has good selectivity to the detection of HCN gas, micro-by analytical calculation quartz crystal
The frequency of vibration changing value of the electrode of balance crystal oscillator, it is achieved the qualitative or quantitative detection to HCN gas.
Quartz crystal microbalance sensor detecting system used in the present invention is made up of three parts.I.e. distribution
System, quartz crystal microbalance sensor detecting system and signal acquiring system.Air distribution system is mainly used in
The concentration of the gases such as regulation HCN, specifically, the method preparation using saturated vapor air purging is the denseest
The HCN gas of degree.Detecting system includes the parts such as calorstat, sensing chamber, injection valve.Gas detection cell
It is positioned in calorstat, after steady air current, by injection valve, HCN gas is loaded into sensing chamber, quartz-crystal
The nickel hydroxide ball of the micron order flower-like structure of the electrode surface load of body microbalance sensor and HCN gas
Interacting, produce the response signal of frequency, the response signal of this frequency is remembered by signal acquiring system
Record, can obtain the important informations such as HCN gas concentration by computational analysis.Concrete experimental result shows,
The electrode of the quartz crystal microbalance sensor that the nickel hydroxide ball of micron order flower-like structure is modified is to HCN gas
Body response rapidly, increase value to the response signal (Δ F) of the frequency of 20ppm HCN gas in 10 seconds
624Hz can be reached, be far superior to the load sample of other kind；Further, the quartz crystal of the present invention
Microbalance sensor is to the response signal of the frequency of HCN gas and to other gas such as acetone, ether, water
Or the response signal of the frequency of the saturated vapor of ethanol etc. is contrary, and the QCM of the present invention is described
The electrode of crystal oscillator has good selectivity to the detection of HCN gas.
The quartz crystal microbalance sensor for quickly detection severe toxicity HCN gas of the present invention has volume
Little, can conveniently be transferred to the advantage in HCN gas-detecting device.Use the hydrogen-oxygen of micron order flower-like structure
Change the electrode of the QCM crystal oscillator that nickel ball is modified, as the electricity of quartz crystal microbalance sensor
Pole, this quartz crystal microbalance sensor is sensitive, for low concentration (20ppm) to the response of HCN gas
HCN gas show good response.
Accompanying drawing explanation
Fig. 1. the X-of the nickel hydroxide ball sample of the micron order flower-like structure prepared by the embodiment of the present invention 1 penetrates
Line diffraction spectrogram.
The scanning of the nickel hydroxide ball sample of the micron order flower-like structure prepared by Fig. 2 a. embodiment of the present invention 1
Electromicroscopic photograph.
The transmission of the nickel hydroxide ball sample of the micron order flower-like structure prepared by Fig. 2 b. embodiment of the present invention 1
Electromicroscopic photograph.
Fig. 3. the nickel hydroxide ball sample of the micron order flower-like structure prepared by the embodiment of the present invention 5 is modified
The electrode of the quartz crystal microbalance sensor single cycle response curve to the HCN gas of 20ppm.
Fig. 4. the nickel hydroxide ball sample of the micron order flower-like structure prepared by the embodiment of the present invention 5 is modified
The electrode of quartz crystal microbalance sensor three round robin curves to the HCN gas of 20ppm.
Fig. 5. the nickel hydroxide ball sample of the micron order flower-like structure prepared by the embodiment of the present invention 5 is modified
The electrode of quartz crystal microbalance sensor to acetone, ether, water, ethanol the response of saturated vapor bent
Line.
Detailed description of the invention
Embodiment 1.
At room temperature take 1～2 gram of nickel nitrate be dissolved in the resistivity of 20～60 milliliters be 18.2M Ω cm go from
In sub-water, it is stirred vigorously to being completely dissolved；The ammonia of 3～10 milliliters is joined in above-mentioned solution, through stirring
Mix and obtain transparence solution；Take the resistance that 0.01～0.3 gram of dodecylbenzene sodium sulfonate is dissolved in 20～60 milliliters
Rate is in the deionized water of 18.2M Ω cm, stirs to being completely dissolved and obtains solution, pours this solution into
In the transparence solution stated, it is stirred vigorously 6～12 hours mix homogeneously and obtains mixed solution；By molten for this mixing
Liquid is transferred in the stainless steel cauldron with politef as liner, seals, is 100～140 DEG C in temperature
Under conditions of keep 6～12 hours, with the deionized water wash 3 that resistivity is 18.2M Ω cm～6 times
The product arrived, is then dried 6～12 by the product after washing under conditions of temperature is 60～90 DEG C
Hour, finally giving jade-green nickel hydroxide ball powder, this nickel hydroxide ball is the flower-shaped knot of micron order
Structure, a diameter of 3～6 μm of the nickel hydroxide ball of gained micron order flower-like structure, and the hydrogen-oxygen of flower-like structure
The thickness of each blade changing nickel ball is 20～30nm.Take the hydrogen-oxygen of a certain amount of gained micron order flower-like structure
Change nickel ball and carry out X-ray diffraction analysis, gained spectrogram and standard spectrogram (JCPDS14-0117) basic
Cause, as shown in Figure 1, it can be determined that obtain is nickel hydroxide product.By a small amount of dried micron order
The nickel hydroxide ball of flower-like structure is scattered in ethanol, and it is scanned the analysis of Electronic Speculum and transmission electron microscope
(Fig. 2 a and Fig. 2 b), analysis result shows that the product obtained is flower-like structure, a diameter of 3～6 μm, group
The thickness becoming unit nanometer sheet (blade) is 20～30nm.
Embodiment 2.
At room temperature take 1～2 gram of nickel nitrate be dissolved in the resistivity of 20～60 milliliters be 18.2M Ω cm go from
In sub-water, it is stirred vigorously to being completely dissolved；The ammonia of 10～17 milliliters is joined in above-mentioned solution, warp
Stirring obtains transparence solution；Take the electricity that 0.01～0.3 gram of dodecylbenzene sodium sulfonate is dissolved in 20～60 milliliters
Resistance rate is in the deionized water of 18.2M Ω cm, stirs to being completely dissolved and obtains solution, pours this solution into
In above-mentioned transparence solution, it is stirred vigorously 6～12 hours mix homogeneously and obtains mixed solution；By this mixing
Solution is transferred in the stainless steel cauldron with politef as liner, seals, in temperature is
Keep 6～12 hours under conditions of 140～170 DEG C, with the deionized water wash that resistivity is 18.2M Ω cm
The product that 3～6 times obtain, is then carried out the product after washing under conditions of temperature is 60～90 DEG C
Being dried 6～12 hours, finally given jade-green nickel hydroxide ball powder, this nickel hydroxide ball is micron
Level flower-like structure, a diameter of 3～6 μm of the nickel hydroxide ball of gained micron order flower-like structure, and flower-shaped knot
The thickness of each blade of the nickel hydroxide ball of structure is 20～30nm.Take a certain amount of flower-shaped knot of gained micron order
The nickel hydroxide ball of structure carries out X-ray diffraction analysis, gained spectrogram and standard spectrogram (JCPDS14-0117)
Basically identical, it can be determined that obtain is nickel hydroxide product.By a small amount of flower-shaped knot of dried micron order
The nickel hydroxide ball of structure is scattered in ethanol, and it is scanned the analysis of Electronic Speculum and transmission electron microscope, analyzes
Result shows that the product obtained is flower-like structure, a diameter of 3～6 μm, component units nanometer sheet (blade)
Thickness be 20～30nm.
Embodiment 3.
At room temperature take 2～3 grams of nickel nitrates be dissolved in the resistivity of 60～80 milliliters be 18.2M Ω cm go from
In sub-water, it is stirred vigorously to being completely dissolved；The ammonia of 10～17 milliliters is joined in above-mentioned solution, warp
Stirring obtains transparence solution；Take the resistance that 0.3～0.5 gram of dodecylbenzene sodium sulfonate is dissolved in 60～80 milliliters
Rate is in the deionized water of 18.2M Ω cm, stirs to being completely dissolved and obtains solution, pours this solution into
In the transparence solution stated, it is stirred vigorously 6～12 hours mix homogeneously and obtains mixed solution；By molten for this mixing
Liquid is transferred in the stainless steel cauldron with politef as liner, seals, is 100～140 DEG C in temperature
Under conditions of keep 6～12 hours, with the deionized water wash 3 that resistivity is 18.2M Ω cm～6 times
The product arrived, is then dried 6～12 by the product after washing under conditions of temperature is 60～90 DEG C
Hour, finally giving jade-green nickel hydroxide ball powder, this nickel hydroxide ball is the flower-shaped knot of micron order
Structure, a diameter of 3～6 μm of the nickel hydroxide ball of gained micron order flower-like structure, and the hydrogen-oxygen of flower-like structure
The thickness of each blade changing nickel ball is 20～30nm.Take the hydrogen-oxygen of a certain amount of gained micron order flower-like structure
Change nickel ball and carry out X-ray diffraction analysis, gained spectrogram and standard spectrogram (JCPDS14-0117) basic
Cause, it can be determined that obtain is nickel hydroxide product.Hydrogen by a small amount of dried micron order flower-like structure
Nickel oxide ball is scattered in ethanol, and it is scanned the analysis of Electronic Speculum and transmission electron microscope, and analysis result shows
Show that the product obtained is flower-like structure, a diameter of 3～6 μm, the thickness of component units nanometer sheet (blade)
It is 20～30nm.
Embodiment 4.
At room temperature take 2～3 grams of nickel nitrates being dissolved in the resistivity of 80～120 milliliters is going of 18.2M Ω cm
In ionized water, it is stirred vigorously to being completely dissolved；The ammonia of 10～17 milliliters is joined in above-mentioned solution,
Agitated obtain transparence solution；Take 0.5～0.8 gram of dodecylbenzene sodium sulfonate and be dissolved in 80～120 milliliters
Resistivity is in the deionized water of 18.2M Ω cm, stirs to being completely dissolved and obtains solution, is fallen by this solution
Enter in above-mentioned transparence solution, be stirred vigorously 6～12 hours mix homogeneously and obtain mixed solution；This is mixed
Close solution and transfer in the stainless steel cauldron with politef as liner, seal, in temperature be
Keep 6～12 hours under conditions of 140～170 DEG C, with the deionized water wash that resistivity is 18.2M Ω cm
The product that 3～6 times obtain, is then carried out the product after washing under conditions of temperature is 60～90 DEG C
Being dried 6～12 hours, finally given jade-green nickel hydroxide ball powder, this nickel hydroxide ball is micron
Level flower-like structure, a diameter of 3～6 μm of the nickel hydroxide ball of gained micron order flower-like structure, and flower-shaped knot
The thickness of each blade of the nickel hydroxide ball of structure is 20～30nm.Take a certain amount of flower-shaped knot of gained micron order
The nickel hydroxide ball of structure carries out X-ray diffraction analysis, gained spectrogram and standard spectrogram (JCPDS14-0117)
Basically identical, it can be determined that obtain is nickel hydroxide product.By a small amount of flower-shaped knot of dried micron order
The nickel hydroxide ball of structure is scattered in ethanol, and it is scanned the analysis of Electronic Speculum and transmission electron microscope, analyzes
Result shows that the product obtained is flower-like structure, a diameter of 3～6 μm, component units nanometer sheet (blade)
Thickness be 20～30nm.
Embodiment 5.
The nickel hydroxide ball of the micron order flower-like structure 7～10 milligrams of embodiments 1 prepared is scattered in
The resistivity of 5～10 milliliters is in the deionized water of 18.2M Ω cm, processes through ultrasonic disperse, is formed all
One scattered suspension；The homogeneous scattered suspension of 4～8 microlitre gained is pipetted with microsyringe, slow
Slow drop coating is 0.196cm in area2The side surface of silver electrode of QCM crystal oscillator；Will
To the silver electrode of the QCM crystal oscillator being loaded with described suspension be placed in drying baker, in
Be dried under room temperature condition 9～12 hours, dried after, then pipette 4～8 microlitre institutes with microsyringe
The homogeneous scattered suspension obtained, slow drop coating is in the opposite side of the silver electrode of QCM crystal oscillator
Surface；The silver electrode of the QCM crystal oscillator being loaded with described suspension obtained is placed in dry
In dry case, it is dried under room temperature condition 9～12 hours, thus obtains quartz crystal microbalance sensor,
Two surfaces of the silver electrode of the QCM crystal oscillator of this quartz crystal microbalance sensor are all modified
There are the nickel hydroxide ball of the micron order flower-like structure of a diameter of 3～6 μm, and the nickel hydroxide ball of flower-like structure
The thickness of each blade be 20～30nm, and the modification amount on two surfaces is all 6～10 micrograms.
Embodiment 6.
The nickel hydroxide ball of the micron order flower-like structure 7～10 milligrams of embodiments 2 prepared is scattered in
The resistivity of 5～10 milliliters is in the deionized water of 18.2M Ω cm, processes through ultrasonic disperse, is formed all
One scattered suspension；The homogeneous scattered suspension of 4～8 microlitre gained is pipetted with microsyringe, slow
Slow drop coating is 0.196cm in area2The side surface of gold electrode of QCM crystal oscillator；Will
To the gold electrode of the QCM crystal oscillator being loaded with described suspension be placed in drying baker, in
Be dried under room temperature condition 9～12 hours, dried after, then pipette 4～8 microlitre institutes with microsyringe
The homogeneous scattered suspension obtained, slow drop coating is in the opposite side of the gold electrode of QCM crystal oscillator
Surface；The gold electrode of the QCM crystal oscillator being loaded with described suspension obtained is placed in dry
In dry case, it is dried under room temperature condition 9～12 hours, thus obtains quartz crystal microbalance sensor,
Two surfaces of the gold electrode of the QCM crystal oscillator of this quartz crystal microbalance sensor all obtain
It is modified with the nickel hydroxide ball of the micron order flower-like structure of a diameter of 3～6 μm, and the hydroxide of flower-like structure
The thickness of each blade of nickel ball is 20～30nm, and the modification amount on two surfaces is all 6～10 micrograms.
Embodiment 7.
(1) quartz crystal microbalance sensor of embodiment 5 is placed in the sensing chamber of severe toxicity gas HCN
In；
(2) in the sensing chamber described in step (1), the air of 800mL/min flow is passed to, by joining
The computer having signal acquiring system records shaking of the electrode by the QCM crystal oscillator in sensing chamber
The response signal of the frequency that dynamic frequency change produces；
(3) passing to flow in the sensing chamber of step (2) is 800mL/min, and concentration is 20ppm's
HCN gas, records by the quartz crystal in sensing chamber by being furnished with the computer of signal acquiring system simultaneously
The response signal of the frequency that the frequency of vibration change of the electrode of micro-balance crystal oscillator produces；
(4) shaking of the electrode of the QCM crystal oscillator of comparative analysis step (2) and step (3)
Dynamic frequency changes, and the frequency of vibration of the electrode of the QCM crystal oscillator of step (3) rises rapidly,
In 10 seconds, the increase value to the response signal (Δ F) of the frequency of 20ppm HCN gas can reach 624Hz,
Determine the existence of HCN gas.
The HCN gas that concentration is 20ppm is shown excellent by prepared quartz crystal microbalance sensor
Good response, testing result is as shown in Figure 3, Figure 4.Fig. 3 shows: after HCN gas is passed through,
On the frequency of vibration of the electrode of the QCM crystal oscillator of this quartz crystal microbalance sensor is rapid
Rising, in 10 seconds, the increase value of frequency reaches 624Hz, and in 25 seconds, the increase value of frequency reaches 825Hz.The most such as
This, this quartz crystal microbalance sensor has good restorative, after three cycle detection, frequently
The response signal of rate can recover, as shown in Figure 4 well.
By the quartz crystal microbalance sensor of embodiment 5, respectively under conditions of temperature is 25 DEG C
The saturated vapor reaching saturated acetone, ether, water, ethanol etc. carries out sensing response detection, detection knot
Fruit is as shown in Figure 5.Be can be seen that through the quartz crystal that nickel hydroxide ball is modified by sensing response curve
The electrode of the QCM crystal oscillator of microbalance sensor is to saturated acetone, ether, water, ethanol
Deng saturated vapor response rapidly, restorative good, and the corresponding signal of gained is contrary with the signal of HCN,
The QCM crystal oscillator of the quartz crystal microbalance sensor that this explanation is modified through nickel hydroxide ball
Electrode HCN is had high selective feature.
Claims (8)
1., for detecting a quartz crystal microbalance sensor for HCN gas, it is characterized in that: at quartz
Two surfaces of the electrode of the QCM crystal oscillator of crystal microbalance sensor are all modified with a diameter of
The nickel hydroxide ball of the micron order flower-like structure of 3～6 μm, and each blade of flower-like structure nickel hydroxide ball
Thickness be 20～30nm；
Described is to be prepared into by following steps for detecting the quartz crystal microbalance sensor of HCN gas
Arrive:
(1) the nickel hydroxide ball of the micron order flower-like structure of a diameter of 3～6 μm of 7～10 milligrams is scattered in
In the deionized water of 5～10 milliliters, ultrasonic disperse forms homogeneous scattered suspension；Described flower-like structure
The thickness of each blade of nickel hydroxide ball be 20～30nm；
(2) taking the 4～8 homogeneous scattered suspensions of microlitre step (1) gained, drop coating is in QCM
One side surface of the electrode of crystal oscillator；
(3) electrode of the QCM crystal oscillator being loaded with described suspension that step (2) is obtained
Being placed in drying baker, after being dried under room temperature condition, then it is homogeneous to take 4～8 microlitre step (1) gained
Scattered suspension, slow drop coating is in the opposite side surface of the electrode of QCM crystal oscillator；
(4) electrode of QCM crystal oscillator step (3) obtained is placed in drying baker, in room temperature
Under the conditions of be dried, all obtain being modified with straight on two surfaces of the electrode of QCM crystal oscillator
Footpath is the nickel hydroxide ball of the micron order flower-like structure of 3～6 μm, and the nickel hydroxide ball of flower-like structure is every
The thickness of one blade is 20～30nm.
Quartz crystal microbalance sensor for detecting HCN gas the most according to claim 1,
It is characterized in that: two surfaces of the electrode of described QCM crystal oscillator are all modified with a diameter of
The nickel hydroxide ball of the micron order flower-like structure of 3～6 μm, the modification amount on two surface is all 6～10 micrograms.
QCM sensing for detecting HCN gas the most according to claim 1 and 2
Device, is characterized in that: the material of the electrode of described QCM crystal oscillator is golden or silver-colored；Described
The area of the electrode of QCM crystal oscillator is 0.196cm2。
Quartz crystal microbalance sensor for detecting HCN gas the most according to claim 1,
It is characterized in that: the nickel hydroxide ball of described micron order flower-like structure is prepared by following steps:
A () takes 1～3 gram of nickel nitrate and is dissolved in the deionized water of 20～120 milliliters, stirring is to being completely dissolved；
B the ammonia of 3～17 milliliters is joined in the solution of step (a) by (), agitated obtain clear solution；
C () takes the dodecylbenzene sodium sulfonate of 0.01～0.8 gram and is dissolved in the deionized water of 20～120 milliliters, stir
Mix to being completely dissolved；
D solution that step (c) is obtained by () is poured in the clear solution that step (b) is prepared, stirring so that it is mixed
Close uniformly；
E solution that step (d) is obtained by () is transferred in the stainless steel cauldron with politef as liner,
Seal, keep 6～12 hours under conditions of temperature is 100～170 DEG C, be washed with deionized and obtain
Product, is then dried the product after washing under conditions of temperature is 60～90 DEG C, obtains micro-
The nickel hydroxide ball powder of meter level flower-like structure, the nickel hydroxide ball of this micron order flower-like structure a diameter of
3～6 μm, and the thickness of each blade of the nickel hydroxide ball of flower-like structure is 20～30nm.
Quartz crystal microbalance sensor for detecting HCN gas the most according to claim 4,
It is characterized in that: the concentration of described ammonia is 25wt%.
6. according to the QCM sensing for detecting HCN gas described in claim 1 or 4
Device, is characterized in that: described deionization resistivity of water is 18.2M Ω cm.
7. the micro-sky of quartz crystal for detecting HCN gas described in a claims 1 to 3 any one
The application of sensor, is characterized in that: the described QCM biography for detecting HCN gas
Sensor is for detecting the HCN gas of low concentration；
The HCN gas of described low concentration be concentration be the HCN gas of 20ppm.
Application the most according to claim 7, is characterized in that, the step of described detection is:
(A) described quartz crystal microbalance sensor is placed in the sensing chamber of severe toxicity HCN gas, so
After pass to the air of 800mL/min flow, record by detecting by being furnished with the computer of signal acquiring system
The response signal of the frequency that the frequency of vibration change of the electrode of the QCM crystal oscillator in room produces；
(B) described quartz crystal microbalance sensor is placed in the sensing chamber of severe toxicity HCN gas, so
After to pass to flow be 800mL/min, concentration is the HCN gas of 20ppm, by being furnished with signals collecting system
The computer of system records the frequency of vibration change of the electrode by the QCM crystal oscillator in sensing chamber and produces
The response signal of raw frequency；
(C) vibration of the electrode of the QCM crystal oscillator of com-parison and analysis step (A) and step (B)
Frequency changes, and the frequency of vibration of the electrode of the QCM crystal oscillator of step (B) rises rapidly, and 10
In second, the increase value to the response signal of the frequency of 20ppm HCN gas reaches 624Hz, it is determined that HCN
The existence of gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410276034.3A CN104048893B (en) | 2014-06-19 | 2014-06-19 | For detecting the quartz crystal microbalance sensor of HCN gas and preparation method thereof and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410276034.3A CN104048893B (en) | 2014-06-19 | 2014-06-19 | For detecting the quartz crystal microbalance sensor of HCN gas and preparation method thereof and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104048893A CN104048893A (en) | 2014-09-17 |
| CN104048893B true CN104048893B (en) | 2017-01-04 |
Family
ID=51502015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410276034.3A Active CN104048893B (en) | 2014-06-19 | 2014-06-19 | For detecting the quartz crystal microbalance sensor of HCN gas and preparation method thereof and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104048893B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105865962B (en) * | 2016-03-15 | 2019-02-01 | 浙江大学 | A kind of wireless QCM-D vapor detection system and method for electromagnetic excitation |
| CN106092802B (en) * | 2016-05-10 | 2019-04-16 | 浙江大学 | A kind of EL-QCM-D array fluid detection system that the sharp electricity of light picks up |
| CN107632065B (en) * | 2016-07-18 | 2019-11-12 | 中国科学院理化技术研究所 | Detect the quartz crystal microbalance sensor and its preparation method and application of the Kocide SD modification of hydrogen cyanide gas |
| CN111999383B (en) * | 2020-09-08 | 2024-02-13 | 崔学晨 | Quartz crystal microbalance and in-situ regeneration method of sensing chip thereof |
| CN114441362A (en) * | 2021-12-31 | 2022-05-06 | 杭州诺蒙微晶生物科技有限公司 | Method for preparing quartz crystal microbalance sensor |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3933340B2 (en) * | 1999-03-30 | 2007-06-20 | 昇 小山 | Multi-channel QCM sensor device |
| CN101988882B (en) * | 2009-08-03 | 2012-04-25 | 中国科学院理化技术研究所 | Quartz crystal microbalance sensor for detecting hydrogen cyanide (HCN) gas, manufacturing method and application thereof |
-
2014
- 2014-06-19 CN CN201410276034.3A patent/CN104048893B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104048893A (en) | 2014-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104048893B (en) | For detecting the quartz crystal microbalance sensor of HCN gas and preparation method thereof and application | |
| Alam et al. | Detection of uric acid based on doped ZnO/Ag 2 O/Co 3 O 4 nanoparticle loaded glassy carbon electrode | |
| Can et al. | Modeling of heavy metal ion adsorption isotherms onto metallophthalocyanine film | |
| Gao et al. | Development of molecularly imprinted polymer films used for detection of profenofos based on a quartz crystal microbalance sensor | |
| CN104181068B (en) | Hydrogen cyanide gas and water vapour are had the quartz crystal microbalance sensor that the cupric oxide of contrary response signal is modified | |
| Zhu et al. | Rational incorporation of covalent organic framework/carbon nanotube (COF/CNT) composites for electrochemical aptasensing of ultra-trace atrazine | |
| CN101988882B (en) | Quartz crystal microbalance sensor for detecting hydrogen cyanide (HCN) gas, manufacturing method and application thereof | |
| CN102408094B (en) | Preparation method for highly repetitive surface enhanced Raman spectrum (SERS) active substrate | |
| CN106560703B (en) | The method for being used to prepare the molecular engram sensor of detection melamine | |
| CN108226244B (en) | For detecting the electrochemical sensor and its preparation method and application of lead ion and/or cadmium ion | |
| CN112414993B (en) | Organic phosphorus Raman detection kit and method | |
| CN105668613A (en) | Fe-doped stannic oxide flower-like nanosphere material with ultrasensitive respiratory sensing performance | |
| Rueda-Holgado et al. | Miniaturized voltammetric stripping on screen printed gold electrodes for field determination of copper in atmospheric deposition | |
| CN103884669A (en) | Preparation method and application of nano-silver probe for detecting mercury ions | |
| Yang et al. | A copper–manganese composite oxide as QCM sensing layers for detection of formaldehyde gas | |
| CN101750442B (en) | Monodispersive bimetal Au/Pt nano-particle modified electrode for detecting mercury in water and preparation method thereof | |
| Guo et al. | A PDMS microfluidic impedance immunosensor for sensitive detection of pesticide residues in vegetable real samples | |
| CN104198714A (en) | Electrochemical immunosensor and preparation and application thereof | |
| Zang et al. | A novel high selectivity chemiluminescence sensor for fenvalerate based on double-sided hollow molecularly imprinted materials | |
| Fu et al. | Application of nickel cobalt oxide nanoflakes for electrochemical sensing of estriol in milk | |
| Farshchi et al. | Electropolymerization of chitosan in the presence of CuNPs on the surface of a copper electrode: an advanced nanocomposite for the determination of mefenamic acid and indomethacin in human plasma samples and prevention of drug poisoning | |
| Eddaif et al. | Calix [4] resorcinarene macrocycles interactions with Cd2+, Hg2+, Pb2+, and Cu2+ cations: a qcm‐i and Langmuir ultra‐thin monolayers study | |
| CN113899805B (en) | Electrochemical sensor for detecting thiabendazole and preparation method and application thereof | |
| Zhou et al. | Piezoelectric sensor for detection of organic amines in aqueous phase based on a polysiloxane coating incorporating acidic functional groups | |
| CN109406603A (en) | A kind of highly selective cadmium ion selection electrode and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |