CN102175764A - Mass chemical sensor and method using functionalized mesoporous material as sensitive material - Google Patents
Mass chemical sensor and method using functionalized mesoporous material as sensitive material Download PDFInfo
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Abstract
The invention relates to a mass type chemical sensor using functionalized mesopores as a sensitive material, a manufacturing method and application, and belongs to the field of micro-nano sensors. The invention is characterized in that the chemical sensor uses an organic functional mesoporous material as a sensitive material and uses a mass transducer as a platform for sensitive detection. The chemical sensor provided by the invention realizes selective adsorption of specific target chemical molecules by using specific organic functional groups of the functionalized mesoporous material, improves the adsorption capacity of the sensitive material to the specific target chemical molecules by using the high specific surface area and high porosity of the functionalized mesoporous material, and converts the adsorption of the functionalized mesoporous material to the specific target chemical molecules into electrical signals to be output by using the mass transducer, thereby realizing the detection of the specific target chemical molecules.
Description
Technical field
The present invention relates to a kind of functional mesoporous mass type chemical sensor, manufacture method and application of sensitive material that be that utilize, belong to the micro-nano sensor field.
Background technology
The high sensitivity chemical sensor has a wide range of applications at aspects such as environmental monitoring, food industry, medical diagnosis, national security as a kind of important biochemistry detection means.In standard GB/T7665-1987, the definition of chemical sensor is " can experience the chemistry amount of regulation and convert the sensor of usable output signal to ".According to this definition, chemical sensor generally is made up of recognition component, inverting element and corresponding circuit.In numerous chemical sensor classifications, the mass type chemical sensor is one of them research focus.The mass type chemical sensor is meant and uses a class chemical sensor that comprises that QCM (Quartz Crystal Microbalance) (QCM), surface acoustic wave (SAW) and resonant-type tiny cantilever beam (resonantmicro-cantilever) etc. adsorb target molecule as mass type transducer (transducer), dependence sensitive thin film.The adsorbance that this class chemical sensor all is based on detected material causes the resonant frequency value of sensor to produce decline, thereby obtains the output response of sensor.According to the principle of work of mass type chemical sensor, under the certain situation of mass type transducer kind and specification, if increase the adsorbance of sensitive thin film to target molecule, the sensitivity that must improve chemical sensor.
Mesoporous material is that a class has the specific surface area height and (can reach 1500m
2/ g), porosity height, aperture homogeneous, aperture are adjustable continuously and the advanced nano material of advantage such as Heat stability is good.In addition, mesoporous material also has the characteristics that the covalent bond grafting of functional group is easily carried out on the surface.Since 1990s age Metaporous silicon dioxide material was found, through years of development, functional mesoporous material had been widely used in fields such as sorbing material, ion-exchange, drug conveying and catalysis.The report that utilizes mesoporous material to make up chemical sensor mainly concentrate on galvanochemistry and fluorescent optical sensor aspect (as Angew.Chem.Int.Ed.2006,45,7202-7208).Do not appear in the newspapers about the research that utilizes functional mesoporous material to make up the mass type chemical sensor.
Mass type chemical sensor of the present invention be to use functional mesoporous as sensitive material, mass type transducer as detection platform, according to functional mesoporous characteristic with some detected material of the alternative absorption of high density functional group of high-ratio surface, high porosity and surface graft, make the resonant frequency value of mass type transducer this principle that descends, realized high-sensitivity detection some detected material (as ammonia, formaldehyde and heavy metal ion etc.).
Summary of the invention
The object of the present invention is to provide a kind ofly to be mass type chemical sensor, manufacture method and the application of sensitive material based on functional mesoporous, described mass type chemical sensor is characterised in that:
A) described chemical sensor uses the organic functional mesoporous material to be sensitive material;
B) described chemical sensor service property (quality) type transducer is the responsive platform that detects;
C) described organic functional is mesoporous is the mesoporous material of introducing organic functional group in nano pore;
D) described organic functional group comprises amido (NH
2), polyamines base, carboxyl (COOH), thiazolinyl (CH=CH
2), sulfydryl (SH), hydroxyl (OH), phenyl (C
6H
5), trifluoromethyl (CF
3), hexafluoroisopropanol base [OH (CF
3)
2], itrile group (CN) or sulfonic group (SO
3H) etc.;
E) described mass type transducer comprises QCM (Quartz Crystal Microbalance), surface acoustic wave or resonant-type tiny cantilever beam.
Chemical sensor functions of use mesoporous material of the present invention is a sensitive material.Functional mesoporous being characterized as sensitive material:
1. described mesoporous material is mesoporous silicon oxide, mesoporous carbon, mesoporous metal and mesopore metal oxide;
2. described mesoporous material form is powder or film;
The method (co-condensation) of the method (post-grafting) of grafting, copolycondensation and bridged bond type organic and inorganic mesoporous material after 3. the introducing method of described organic functional group comprises (periodicmesoporous organosilicas, PMOs);
4. described mesoporous material is to be carried on the mass type transducer with the coating or the method for self assembly
Chemical sensor service property (quality) type transducer of the present invention is the responsive platform that detects.The mass type transducer can be converted into electrical signal output to the absorption of specific objective chemical molecular with functional mesoporous material, thereby realizes the detection to the specific objective chemical molecular.
In sum, the invention has the advantages that
1) organo-functional group on functional mesoporous material surface can be realized the selective adsorption (for example the carboxyl functional group of carboxyl-functional mesoporous material hole surface has the ability of selective adsorption etc. to the ammonia molecule that is alkalescence) to the specific objective chemical molecular;
2) high-specific surface area and the high porosity that have of functional mesoporous material can improve the adsorbance of sensitive material to the specific objective chemical molecular;
3) organo-functional group on functional mesoporous material surface is the covalent bond grafting, has long-time stability.The bond energy of covalent bond is big, makes the organo-functional group difficult drop-off on functional mesoporous material surface, and this feature makes and the stable performance of functional mesoporous material is suitable for long-term use;
4) utilize functional mesoporous material have high specific surface area and high porosity improve sensitive material to the adsorbance of specific objective chemical molecular, utilize the mass type transducer that functional mesoporous material is converted into electrical signal output to the absorption of specific objective chemical molecular, thereby realize detection to the specific objective chemical molecular.
Method of the present invention, easy operating, cheap, can produce in batches, method advanced person, and in the document at home and abroad report is not arranged.
Description of drawings
The chemical sensor that Fig. 1 makes for the present invention is to the detection spectrogram of tens of ppb magnitude ammonias;
The product that Fig. 2 makes for the present invention is to the test spectrogram of tens of ppm magnitude carbon dioxides.
Embodiment
Embodiment 1: be sensitive material, be transducer with the resonant-type tiny cantilever beam with the carboxyl-functional mesoporous silicon dioxide powder, can be used for the mass type chemical sensor of tens of ppb (ppb is that volume ratio is part per billion) magnitude ammonia detection with the method manufacturing of coating.
1. the manufacture method of carboxyl-functional mesoporous silicon dioxide powder: measure 1 milliliter of CES (carbomethoxysilanetriol, sodium salt, 25wt%in water, purchase company in German ABCR) reagent, be dissolved in 30 ml deionized water, with concentration be the concentrated hydrochloric acid of 36wt% regulate this solution the pH value between the 4-5, it is 2 mouthfuls of round-bottomed flasks of 100 milliliters that this solution is placed a volume, standby.Take by weighing the SBA-15 type Metaporous silicon dioxide material (aperture is about 7 nanometers, specific surface area is about 700 square metres of every grams) of about 0.2 gram, add in above-mentioned 2 mouthfuls of round-bottomed flasks, mix with solution.This round-bottomed flask is placed one 70 ℃ oil bath, and back flow reaction is 3 days under the magnetic agitation.After cooling, after the suspension in the round-bottomed flask repeatedly washed after filtration and with deionized water, place 60 ℃ baking oven vacuum drying, can obtain the mesoporous powder of carboxyl-functional.
2. be sensitive material, be transducer with the resonant-type tiny cantilever beam with the carboxyl-functional mesoporous silicon dioxide powder, the method for workmanship type ammonia chemical sensor.The manufacture method of resonant-type tiny cantilever beam is referring to patent of invention: utilize single integrated resistor to realize simultaneously driving and the micromachine cantilever beam (number of patent application: 200910046447.1) of self-cleaning.Take by weighing 10 milligrams of carboxyl-functional mesoporous silicon dioxide powders, (ultrasonic instrument is purchased in the imperial Electronics Equipment Co., Ltd of last hypo, model: USC-202) be scattered in 1 ml deionized water, make the suspension of carboxyl-functional mesoporous silicon oxide with ultrasound wave.(purchase company at optical microscope in Leica, model: DM4000), utilize micromanipulation system (to purchase company in Eppendorf, model: (surface covered is about 100 microns * 100 microns PatchMan NP2) suspension of carboxyl-functional mesoporous silicon oxide accurately to be coated on the surface of resonant-type tiny cantilever beam device, the consumption of mesoporous material is about 20 nanograms, mesoporous consumption is every square metre of 2 gram on the unit area), place 80 ℃ baking oven to wear out 2 hours, can make with the carboxyl-functional mesoporous silicon oxide is sensitive material, with the resonant-type tiny cantilever beam is the mass type chemical sensor of transducer.
3. the mass type chemical sensor is to the test of ammonia: it is that 99.999% high pure nitrogen is purchased in Shanghai Pujiang special gas company limited that the concentration of using is purchased in Dalian Da Te gas company limited, purity as the ammonia standard gas of 10ppm.With ammonia standard gas after utilizing high pure nitrogen to be diluted to prescribed concentration in the gas calibration device (purchasing) in State Standard Matter Research Centre, feed mass type chemical sensor detection cell, (purchase company, model: 53131A) and the resonant frequency value of phase-locked loop circuit synchronous acquisition sensor with frequency meter in Agilent.Based on acid-base reaction principle (being between carboxyl function group and the alkaline ammonia on mesoporous material surface stronger acid-base function to be arranged), the functional mesoporous earth silicon material that sensor surface has high-specific surface area will adsorb a large amount of ammonia molecules, the ammonia molecule of these absorption will make the resonance frequency of sensor produce reduction, can carry out the scene to ammonia by the resonance frequency of detecting sensor and detect in real time.Accompanying drawing 1 has write down the testing result of sensor to tens of ppb (ppb is that volume ratio is part per billion) magnitude ammonia: when test pool feeds after concentration is the ammonia of 200ppb, and sensor its resonance frequency after about 90 seconds descend about 7 hertz (noise level of ratio sensor is big more than 15 times); Sensor is approximately 40 hertz to the response of 1000ppb ammonia, is about 5 minutes release time.
Embodiment 2: be sensitive material, be transducer with the resonant-type tiny cantilever beam with the functional amido mesopore film, can be used for the mass type chemical sensor that tens of ppm (ppm be volume ratio be 1,000,000/) magnitude carbon dioxide detects with the method manufacturing of self assembly.
1. be sensitive material, be transducer with the resonant-type tiny cantilever beam with the functional amido mesopore film, the method for workmanship type carbon dioxide chemical sensor.The used resonant-type tiny cantilever beam of present embodiment is with embodiment 1.The manufacture method of functional amido mesopore film is a step copolycondensation method: measure 41.2 milliliters of TEOS (positive tetraethyl orthosilicate, analyze pure, purchase in Chemical Reagent Co., Ltd., Sinopharm Group), 40 milliliters of absolute ethyl alcohols, 1 microlitre concentration are concentrated hydrochloric acid and 4.2 ml deionized water of 36wt%, add a volume successively and be in 500 milliliters the beaker, in 60 ℃ oil bath, insulation is 90 minutes under the magnetic agitation.Add 160 milliliters of absolute ethyl alcohols, stir.Add 5 milliliters of APTES (the 3-aminopropyl triethoxysilane is purchased the company in Sigma-Aldrich) and 2 ml deionized water successively, in ice-water bath, dropwise add the concentrated hydrochloric acid that 4.8 ml concns are 36wt% under (0 ℃) vigorous stirring.Add 95 milliliters of absolute ethyl alcohols and 8.4 gram CTAB (hexadecyl trimethyl ammonium bromide is purchased the company in Sigma-Aldrich) successively, stirring, standby (this precursor solution is labeled as-NH
2Storing solution).Under room temperature, constant humidity (25 ℃, 60%RH) condition, resonant-type tiny cantilever beam is fixed on the optical microscope, and general-NH
2Storing solution sucks in the kapillary of micromanipulation system (the instrument model is with embodiment 1), adjusts the position, and resonant-type tiny cantilever beam is inserted in the kapillary, and resonant-type tiny cantilever beam is submerged in the kapillary-NH fully
2In the storing solution, replace method (rate of pulling the is approximately 10 microns per seconds) general-NH that draws (dip-coating) with dipping afterwards
2Storing solution evenly is coated on the surface (surface covered is about 100 microns * 100 microns, and the thickness of film is about 500 nanometers) of resonant-type tiny cantilever beam.To be coated with-NH
2It is that the constant humidity cabinet of 60%RH carries out burin-in process that the resonant-type tiny cantilever beam of storing solution film places humidity, take out after 48 hours, with a large amount of absolute ethyl alcohols (about 200 milliliters) flushing resonant-type tiny cantilever beam, be sensitive material, be the mass type carbon dioxide chemical sensor of transducer with the resonant-type tiny cantilever beam to remove the remaining CTAB in resonant-type tiny cantilever beam surface, can make with the functional amido mesopore film.
2. the mass type chemical sensor is to the test of carbon dioxide: concentration is that 99.999% high-purity carbon dioxide gas is purchased in Shanghai Pujiang special gas company limited.Adopt the method for static distribution, at first sensor being placed a volume is 40 liters organic glass test box, with the resonant frequency value of frequency meter (purchasing the company in Agilent, model 53131A) and phase-locked loop circuit synchronous acquisition sensor.The baseline for the treatment of sensor steadily after, high-purity carbon dioxide gas is injected the organic glass test box, mix the carbon dioxide test atmosphere that can obtain prescribed concentration.Based on acid-base reaction principle (being between the primary amine amido functional group on mesoporous material surface and the acid carbon dioxide stronger acid-base function to be arranged), the functional mesoporous material that sensor surface has high-specific surface area will adsorb a large amount of carbon dioxide molecules, the carbon dioxide molecule of these absorption will make the resonant frequency value of sensor produce reduce, and the resonant frequency value by detecting sensor can detect carbon dioxide.Accompanying drawing 2 has write down the testing result of sensor to tens of ppm magnitude carbon dioxide: when test pool feeds after concentration is the carbon dioxide of 500ppm, and sensor its resonance frequency after about 10 seconds descend about 6 hertz (noise level of ratio sensor is big more than 12 times); Sensor is approximately 40 hertz to the response of 2500ppm carbon dioxide, and release time was less than 5 minutes.
Embodiment 3: be sensitive material, be transducer with QCM (Quartz Crystal Microbalance) (QCM) with mercapto-functionalized mesoporous silicon dioxide powder, can be used for every liter of hundreds of microgram (μ gL with the method manufacturing of coating
-1) the mass type chemical sensor that detects of magnitude metal mercury ions.
Be sensitive material, be transducer with QCM with mercapto-functionalized mesoporous silicon dioxide powder, the method for workmanship type heavy metal ion chemical sensor.The QCM that present embodiment is used, its resonance frequency is 10M (purchasing in the Beijing ChenJing Electronics Co., Ltd).Take by weighing 10 milligrams of mercapto-functionalized mesoporous silicon dioxide powders, in 1 ml deionized water, make the suspension of mercapto-functionalized mesoporous silicon oxide with ultrasonic dispersing.With accurate micropipettor (purchase the company in the gloomy Gilson of French gill, specification is the 0-20 microlitre) draw 20 microlitre suspensions evenly drip be applied to QCM go up (drip and be coated with area and be about 20 square millimeters, on the unit area mesoporous consumption be 2 grams/square metre)), oven dry.With the another side silicone rubber seal of QCM, the resonant frequency value with frequency meter (purchasing the company in Agilent, model 53131A) and oscillatory circuit synchronous acquisition sensor promptly makes mass type heavy metal ion chemical sensor.This mass type chemical sensor can every liter of (μ gL of logarithm hectogamma
-1) the magnitude metal mercury ions carries out real-time, online detection.
Embodiment 4: be sensitive material, be transducer with the resonant-type tiny cantilever beam with the functional mesoporous titanic oxide material of three amidos, can be used for the mass type chemical sensor that ppm (ppm be volume ratio be 1,000,000/) magnitude formaldehyde detects with the method manufacturing of coating.
Since formaldehyde gas can react with amine compound (for example number of patent application be documents such as 200910162558.9 and 200810196267.7 all report use amido derivative to make the formaldehyde absorbing agent), simultaneously in order to increase the sensitivity of sensor PARA FORMALDEHYDE PRILLS(91,95), the present invention choose triamido silanization coupling agent (for example 3-[2-(2-Aminoethylamino) ethylamino] propyltrimethoxysilane, purchase company in Sigma-Aldrich) mesoporous TiO 2 is carried out functionalization, obtain the mesoporous TiO 2 sensitive material of polyamines base functionalization.Using 3-[2-(2-Aminoethylamino) ethylamino] propyltrimethoxysilane silanization coupling agent carries out the sensitive material of functionalization, it is characterized in that all having 3 amidine functional groups on each strain functionalization carbochain of material surface, these 3 amidine functional groups all are the responsive sites of PARA FORMALDEHYDE PRILLS(91,95) molecule.Employing is with the identical method of embodiment 1, this sensitive material is coated on the surface of resonant-type tiny cantilever beam, and (surface covered is about 100 microns * 100 microns, mesoporous consumption is about 20 nanograms, mesoporous consumption is about every square metre of 2 gram on the unit area), promptly make the mass type chemical sensor that can be used for the detection of ppm magnitude formaldehyde.
Embodiment 5: be sensitive material, be transducer with the resonant-type tiny cantilever beam with the hydroxyl functional meso-porous carbon material, humidity is changed the mass type chemical sensor of sensitivity with the method manufacturing of coating.
Because acticarbon can planar water steam, therefore be often used as drying agent.But commercial acticarbon lacks order, pore diameter distribution heterogeneity aspect micromechanism, and pore capacities is not high enough.Compare with commercial acticarbon, mesoporous carbon has advantages such as even aperture distribution, order height, pore capacities are big, Stability Analysis of Structures.It is raw material that the present invention chooses mesoporous carbon, through concentrated nitric acid oxidation, make the mesoporous carbon surface have more can with the hydroxyl of hydrone effect, make the hydroxyl functional mesoporous carbon that can be used for Humidity Detection.Employing is with the identical method of embodiment 1, and the hydroxyl functional mesoporous carbon is coated on the surface of resonant-type tiny cantilever beam, promptly makes the mass type chemical sensor that humidity is changed responsive (the relative humidity variations amount that can differentiate reaches 1%).Its manufacture method is as follows:
A) take by weighing 0.1 gram mesoporous carbon, adds 20 milliliters of red fuming nitric acid (RFNA)s (mass concentration is about 70%), under the room temperature ultrasonic 2 hours, after filtration, deionized water wash is near neutrality, 60 ℃ of steps such as vacuum drying, can obtain the mesoporous carbon of hydroxyl functionalization.
B) (the used resonant-type tiny cantilever beam of present embodiment is with embodiment 1 for fear of resonant-type tiny cantilever beam.) to the absorption of water vapour, resonant-type tiny cantilever beam of the present invention at first carries out hydrophobization to be handled: 100 microlitres, 17 fluorine certain herbaceous plants with big flowers base trimethoxy silane (heptadecafluorodecyltrimethoxysilane, FAS-17, purchase company in Sigma-Aldrich) be dissolved in 10 milliliters of ethanol, make FAS-17 solution.Micro-cantilever is immersed in this solution fully, and reaction was used ethanol and deionized water rinsing 5 minutes respectively after 2 hours under the room temperature.Can obtain hydrophobic resonant-type tiny cantilever beam.
C) take by weighing the mesoporous carbon powder of 10 milligrams of hydroxyl functionalizations, (ultrasonic instrument is purchased in last hypo dragon Electronics Equipment Co., Ltd, model: USC-202) be scattered in 1 ml deionized water, make the suspension of hydroxyl functional mesoporous carbon with ultrasound wave.
D) adopt identical method with embodiment 1, the hydroxyl functional mesoporous carbon is coated on the surface of hydrophobic resonant-type tiny cantilever beam, and (surface covered is about 100 microns * 100 microns, mesoporous consumption is about 20 nanograms, mesoporous consumption is about every square metre of 2 gram on the unit area), promptly make the mass type chemical sensor that can be used for Humidity Detection.
Claims (8)
1. one kind is the mass type chemical sensor of sensitive material based on functional mesoporous material, it is characterized in that:
A) described chemical sensor uses the organic functional mesoporous material to be sensitive material;
B) described chemical sensor service property (quality) type transducer is the responsive platform that detects;
C) described organic functional mesoporous material is a mesoporous material of introducing organic functional group in nano pore;
D) described organic functional group comprises amido, polyamines base, carboxyl, thiazolinyl, sulfydryl, hydroxyl, phenyl, trifluoromethyl, hexafluoroisopropanol base, itrile group or sulfonic group;
E) described mass type transducer comprises QCM (Quartz Crystal Microbalance), surface acoustic wave or resonant-type tiny cantilever beam.
2. mass type chemical sensor according to claim 1 is characterized in that described mesoporous material is mesoporous silicon oxide, mesoporous carbon, mesoporous metal and mesopore metal oxide.
3. mass type chemical sensor according to claim 1 and 2 is characterized in that described mesoporous material form is powder or film.
4. mass type chemical sensor according to claim 1 is characterized in that the introducing method of described organic functional group comprises the method for back grafting, the method or the bridged bond type organic and inorganic mesoporous material of copolycondensation.
5. make the method for the mass type chemical sensor described in claim 1-4, it is characterized in that with the carboxyl-functional mesoporous silicon dioxide powder be sensitive material, with the resonant-type tiny cantilever beam is transducer, with the step of application pattern fabricating quality type chemical sensor is:
1. make the carboxyl-functional mesoporous silicon dioxide powder
A) measure 1 milliliter of CES reagent, be dissolved in 30 ml deionized water, with the mass percentage concentration be the hydrochloric acid of 36wt% regulate this solution the pH value between the 4-5, it is 100 milliliters twoport round-bottomed flask that this solution is placed a volume, standby;
B) take by weighing the SBA-15 type Metaporous silicon dioxide material of 0.2 gram, and join in the above-mentioned twoport round-bottomed flask, mix with solution;
C) this twoport round-bottomed flask is placed one 70 ℃ oil bath, back flow reaction is 72 hours under the magnetic agitation; After cooling, after the suspension in the round-bottomed flask repeatedly washed after filtration and with deionized water, place 60 ℃ baking oven vacuum drying, can obtain the mesoporous powder of carboxyl-functional;
2. make with the carboxyl-functional mesoporous silicon dioxide powder and be sensitive material, be the mass type chemical sensor of transducer with the resonant-type tiny cantilever beam
A) take by weighing 10 milligrams of carboxyl-functional mesoporous silicon dioxide powders, in 1 ml deionized water, make the suspension of carboxyl-functional mesoporous silicon oxide with ultrasonic dispersing;
B) be under the optical microscope of DM4000 in model, utilize micromanipulation system the suspension of carboxyl-functional mesoporous silicon oxide accurately to be coated on the surface of resonant-type tiny cantilever beam device, surface covered is 100 microns * 100 microns, the consumption of mesoporous material is 20 nanograms, the consumption of mesoporous material is every square metre of 2 gram on the unit area, place 80 ℃ aging 2 hours of baking oven, can make with the carboxyl-functional mesoporous silicon oxide and be sensitive material, be the mass type chemical sensor of transducer with the resonant-type tiny cantilever beam;
Wherein, described CES reagent is that the carbomethoxysilanetriol sodium salt dissolves the reagent that forms in water, and mass percentage concentration is 25wt%, and the aperture of described SBA-15 type Metaporous silicon dioxide material is 7nm, and specific surface area is 700 square metres/every gram; Described micromanipulation system model is PatchMan NP2.
6. make method, it is characterized in that being sensitive material, being transducer with the resonant-type tiny cantilever beam, be with the step of the method workmanship type chemical sensor of self assembly with the functional amido mesopore film as the described mass type chemical sensor of claim 1-4:
1. with the functional amido mesopore film manufacturing of sensitive material
A) measure 41.2 milliliters analyze pure TEOS, 40 milliliters of absolute ethyl alcohols, 1 microlitre mass percentage concentration are concentrated hydrochloric acid and 4.2 ml deionized water of 36wt%, join a volume successively and be in 500 milliliters the beaker;
B) then in 60 ℃ oil bath, insulation is 90 minutes under the magnetic agitation; Add 160 milliliters of absolute ethyl alcohols again, stir;
C) add 5 milliliters of APTES and 2 ml deionized water successively, the concentrated hydrochloric acid that dropwise to add 4.8 milliliters of mass percentage concentration under the vigorous stirring in ice-water bath be 36wt%.Add 95 milliliters of absolute ethyl alcohols and 8.4 gram CTAB successively, it is standby to stir, and this precursor solution is labeled as-NH
2Storing solution;
2. the making of mass type chemical sensor
A) under the room temperature of 25 ℃ and 60%RH, constant humidity condition, resonant-type tiny cantilever beam is fixed on the optical microscope; And the sensitive material solution that 1. above-mentioned steps is prepared sucks in the kapillary of micromanipulation system, adjusts the position, and resonant-type tiny cantilever beam is inserted in the kapillary, and resonant-type tiny cantilever beam is submerged in the kapillary-NH fully
2In the storing solution;
B) be that 10 little meter per second dippings are for the method general-NH that draws with the rate of pulling afterwards
2Storing solution evenly is coated on the surface of resonant-type tiny cantilever beam, and surface covered is 100 microns * 100 microns, and the thickness of film is 500 nanometers;
C) will be coated with-NH
2It is that the constant humidity cabinet of 60%RH carries out burin-in process that the resonant-type tiny cantilever beam of storing solution film places humidity, take out after 48 hours, with a large amount of absolute ethyl alcohol flushing resonant-type tiny cantilever beams, be sensitive material, be the mass type carbon dioxide chemical sensor of transducer with the resonant-type tiny cantilever beam to remove the remaining CTAB in resonant-type tiny cantilever beam surface, can make with the functional amido mesopore film.
7. press the application of each described mass type chemical sensor of claim 1-4, it is characterized in that utilizing functional mesoporous material have high specific surface area and high porosity improve sensitive material to the adsorbance of specific objective chemical molecular, utilize the mass type transducer that functional mesoporous material is converted into electrical signal output to the absorption of specific objective chemical molecular, thereby realize detection to the specific objective chemical molecular.
8. by the described application of claim 7, it is characterized in that:
1. being sensitive material with the carboxyl-functional mesoporous silicon dioxide powder, is that the quality chemical sensor of transducer can be used for tens of PPb magnitude ammonias detections with the resonant-type tiny cantilever beam;
2. be that sensitive material is a transducer with the resonant mode semi-girder with the functional amido dielectric film, be used for the carbon dioxide detection of tens of PPm magnitudes with the quality chemical sensor of self-assembling method making;
3. being sensitive material to dredge basic functionalized SiO 2 powder, is transducer with the QCM (Quartz Crystal Microbalance), and the quality chemical sensor that application pattern is made is used for every liter of hundreds of microgram magnitude metal mercury ions and detects;
4. being sensitive material with the functional mesoporous silicon-dioxide powdery of triamido, is transducer with the resonant-type tiny cantilever beam, is used for the formaldehyde detection of PPm magnitude with the quality chemical sensor of application pattern making;
5. being sensitive material with the hydroxyl functional meso-porous carbon material, is transducer with the resonant-type tiny cantilever beam, and the quality chemical sensor made from the method for coating is used for Humidity Detection.
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