CN102175553B - Gas sensor based on bacteria cellulose and manufacturing method thereof - Google Patents
Gas sensor based on bacteria cellulose and manufacturing method thereof Download PDFInfo
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- CN102175553B CN102175553B CN 201010602840 CN201010602840A CN102175553B CN 102175553 B CN102175553 B CN 102175553B CN 201010602840 CN201010602840 CN 201010602840 CN 201010602840 A CN201010602840 A CN 201010602840A CN 102175553 B CN102175553 B CN 102175553B
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Abstract
The invention relates to a gas sensor based on bacteria cellulose, and the gas sensor provided by the invention comprises a quartz crystal microbalance compound electrode, a quartz substrate and a sensing material, wherein the quartz crystal microbalance compound electrode is arranged in the center of the quartz substrate; the quartz crystal microbalance compound electrode comprises a quartz crystal microbalance electrode and a film; the film is adhered to the surface of the quartz crystal microbalance electrode; the sensing material is scattered in the film; and the film is a bacteria cellulose film. The invention also relates to a method for manufacturing the gas sensor based on bacteria cellulose, and the method provided by the invention comprises the following steps: acquiring a uniformly scattered mixture by homogenizing the bacteria cellulose and distilled water; coating the mixture on the clean and dry surface of the quartz crystal microbalance electrode; and coating the sensing material and then drying, thereby acquiring the sensor. The gas sensor provided by the invention has the advantages that the cost is low, the sensitivity is high, the reusability is achieved, the stability is durable, the selectivity is excellent; and the method provided by the invention is simple in manufacturing process and easy for realization of batch production.
Description
Technical field
Background technology
As everyone knows, toxic gas detection is used very extensive at daily life, industry, agricultural and field of Environment Protection, especially at building materials, in household products and the various industrial processes, along with people improve gradually to environmental protection and health problem degree of concern, highly sensitive gas detection method will be very important.And the method for traditional detection toxic gas spectrophotometric method for example, vapor-phase chromatography, the detection method sensitivity such as Electrochemical Detection are lower, and need large-scale expensive complicated laboratory equipment, complex operation, consuming time longer, can not satisfy the demand of Monitor in time on a large scale, and testing result is subjected to the impact of other gas easily.Therefore, be necessary to formulate one highly sensitive, easy, fast, can continuous monitoring detect the method for toxic gas.
QCM (Quartz Crystal Microbalance) (QCM) sensor is a kind of microsensor of nanogram level mass-sensitive type, its principle mainly is the piezoelectric effect according to quartz crystal, when quartz crystal is applied alternating voltage, quartz crystal will vibrate, when the natural frequency of the frequency of oscillatory circuit and quartz crystal is consistent, just produce resonance, this moment, vibration was the most stable.Quartz crystal oscillator has stable natural frequency, and under certain condition, when other material of quartz crystal oscillator adsorption, the natural frequency of quartz crystal oscillator changes with the nanogram magnitude quality size variation that causes after adsorbing.Qcm sensor is exactly according to this principle, do one deck sensitive thin film at strand DNA on Surface of Quartz crystal, utilize the interaction of sensitive thin film and test substance, the concentration signal of test substance is converted into frequency signal to be detected, it has highly sensitive, and the response time is short, and persistence is good, reversibility and the advantage such as easy to operate, the aspects such as the mensuration of microcomponent and analysis are widely applied in Tiny Mass detection, toxic gas detection, solution.
The sensitive membrane of using in the QCM gas sensor is mainly the metallic films such as organic polymer sensitive membrane, metal-oxide film, Pt etc.Wherein with the organic polymer sensitive thin film use at most, coating method commonly used has cotton balls swabbing process, syringe drop-coating, spraying process, dipping method etc.And according to the mechanism of adhesion, be coated with intermembranous adhesion mainly from the acting force between the molecule---Van der Waals force, the inner polymer polarity group that forms of class coating material, as-OH base or-the COOH base, produce under the effect of Van der Waals force or Hyarogen-bonding with the polar molecule on quartz wafer surface and to adhere to balance, form adhesion.Therefore, class coating material must adapt with the polarity on quartz wafer surface, only has both mutually to mate, and just can obtain preferably adhesion.The sensitive coating film is to be equal to tested organic molecule by hydrogen bond, polar molecule, dispersion force and hole power or chemical reaction to interact, thereby tested organic molecule is carried out quality Identification.
Electrostatic spinning nano fiber mainly contains two kinds of methods in sensor application: the first is to adopt to carry out Electrospun such as functional polymers such as PAA (polyacrylic acid), PANI (polyaniline) and obtain the nanofiber with inducing function, and with the Electrospun nanofiber directly as the sensing element of sensor, this manufacturing process is comparatively simple, the sensor response time that makes is very fast, sensitivity is higher, and has preferably bio-compatibility; The second be with the Electrospun nanofiber as template, then deposit corresponding inductive material and carry out chemical modification at fiber surface, thereby make the micro nano structure with sensing characteristics." Nanofibrous polyethyleneimine membranes as sensitive coatings for quartz crystal microbalance-based formaldehyde sensors " prepared detection limit by the polyethyleneimine film coating QCM electrode that adopts the Static Spinning acquisition is the formaldehyde sensor of 10ppm; " Electrospun nanofibrous membranes coated quartz crystal microbalance as gas sensor for NH
3Detection " prepare the nanofiber that diameter is 100-400nm by electrostatic spinning PVA and PAA mixed solution, and it is deposited on to have prepared detection limit on the QCM electrode be the ammonia gas sensor of 50ppm.Electrostatic spinning adopts the shower nozzle spining technology, and process is high to outside conditional request, and properties of product are subject to temperature easily, humidity is waited for impact, and spinning efficiency is lower, is difficult for realizing industrial-scale production; Solvent evaporates is very fast in spinning process, is difficult to control the volatilization of toxic solvent, causes environmental pollution, and unfavorable to staff's health; If electrostatic spinning does not change gathering-device in addition, generally can only obtain the nonwoven fabrics without orientation, intensity is low, need just can further use after the aftertreatment, and the spinning of many shower nozzles is difficult to realize because of electrical charge rejection.
Present stage, electrostatic spinning gained nanofiber diameter generally was about 100nm～800nm, along with reducing of fibre diameter, its specific surface area will increase, and the specific surface area of sensing material is the key factor that affects qcm sensor sensitivity, the specific surface area increase will further increase the adsorption site of detected gas, will improve largely transducer sensitivity if therefore can adopt the following nano material of fibre diameter 100nm to make up sensing layer.
Summary of the invention
The purpose of this invention is to provide a kind of gas sensor based on bacteria cellulose, the present invention adopts to have the cancellated bacteria cellulose nano material of 3 D stereo and is deposited on the QCM (Quartz Crystal Microbalance) electrode surface and obtains combination electrode, then combining with sensing material forms a kind of sensitive membrane that is deposited on the QCM (Quartz Crystal Microbalance) electrode surface, obtains sensor thereby make up.Bacteria cellulose fibre is a kind of biosynthetic nanofiber; have unique physical and chemical performance and mechanical property; high-crystallinity, high moisture holding capacity, Nanostructure Network, high-tensile and elastic modulus and excellent biocompatibility and biodegradability; accomplish scale production at present; having solved electrostatic spinning nano fiber yields poorly; a difficult problem that is difficult to suitability for industrialized production, prospect is widely used.Its diameter is about 30-60nm, thereby deposit at the QCM (Quartz Crystal Microbalance) electrode with adhesion such as the polar molecule generation Van der Waals force of strand DNA on Surface of Quartz crystal, hydrogen bonds, the pore diameter distribution and the superhigh specific surface area that recycle its meticulous tridimensional network, Nano grade (are about 50m
2/ g), so that sensing material enters the inside of bacteria cellulose porous structure easily, more contact with the nanometer fento, the great amount of hydroxy group that contains by the fento surface is as avtive spot, with sensing material generation physisorption or chemical action, thereby prepare the sensitive membrane of high-specific surface area at the QCM (Quartz Crystal Microbalance) electrode.Therefore, can increase considerably the adsorption reaction site of detected gas, in reality detects with the sensitivity that greatly improves sensor after pick-up unit combines.Contain a large amount of highly active hydroxyls just because of the bacteria cellulose surface, mechanical property excellent (elastic modulus is more than ten times of general vegetable fibre), the wide performance that waits excellence of flexibility (adaptability) of operation, so it is low, highly sensitive, reusable that this transducer production method has a cost, long-time stability and selectivity are good, preparation technology is simple, realizes easily mass production, has solved the deficiency of at present existing gas detection method.
Such as the QCM formaldehyde gas sensor, because formaldehyde is the metastable material of a kind of chemical property, in air, can be formic acid in conjunction with water and carbon dioxide conversion, thereby the faintly acid of showing, therefore when the preparation sensitive membrane, can select amine substance, macromolecular material with the amido atomic group, the sensing material of alkalescent material, such as the polypropylene-base amine hydrochlorate, polyethyleneimine, triethanolamine etc., by drip be coated in the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose after, utilize the interaction of hydrogen bond of great amount of hydroxy group group that BC nanofiber surface exists and amine groups to prepare the sensitive membrane of the high-specific surface area that sticks to the QCM (Quartz Crystal Microbalance) electrode surface, thereby so that the adsorption site of this sensor PARA FORMALDEHYDE PRILLS(91,95) improves greatly, its detection limit can reach 30PPb in practical operation.
A kind of gas sensor based on bacteria cellulose of the present invention, comprise QCM (Quartz Crystal Microbalance) combination electrode, quartz substrate and sensing material, described QCM (Quartz Crystal Microbalance) combination electrode places quartz substrate central authorities, described QCM (Quartz Crystal Microbalance) combination electrode is comprised of QCM (Quartz Crystal Microbalance) electrode and film, described film is attached at the QCM (Quartz Crystal Microbalance) electrode surface, described sensing material is dispersed in the film, and described film is bacteria cellulose film.
A kind of gas sensor based on bacteria cellulose of the present invention, combination electrode wherein refers to the adhesion such as the polar molecule generation Van der Waals force that utilizes a large amount of hydroxyl in bacteria cellulose fibre surface and ehter bond and strand DNA on Surface of Quartz crystal and Hyarogen-bonding, thereby at QCM (Quartz Crystal Microbalance) electrode surface deposition one deck bacteria cellulose film, its preparation method comprises following implementation step:
(1) dries up or oven dry or natural drying for subsequent use at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and with nitrogen.Be that 1: 1～1: 5 bacteria cellulose and distilled water mix with mass volume ratio, and at room temperature homogenous disperse obtain homodisperse bacteria cellulose aqueous mixtures, such as using hollander or homogenizer with rotating speed 5000-15000r/min making beating 5-20min.
(2) with micro-pipette the bacteria cellulose aqueous mixtures in the 10-50 μ L step (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), drying obtains combination electrode.
A kind of gas sensor based on bacteria cellulose of the present invention, sensitive membrane wherein refers to drip at above-mentioned combination electrode and is coated with sensing material, utilize a large amount of hydroxyl in bacteria cellulose fibre surface and sensing material to form hydrogen bond action, sensing material is evenly distributed in the bacteria cellulose nanofiber three-dimensional net structure, thereby obtains adhering to the sensitive membrane on the combination electrode.The implementation step of its preparation method is coated onto on the combination electrode for massfraction 0.05-3wt% sensing material water solution 2-200 μ L is dripped, in 20-30 ℃ of lower dry 12-24h.
The using method of a kind of gas sensor based on bacteria cellulose of the present invention, implementation step is mainly: sensor obtained above is placed pick-up unit, by syringe injected gas sample in the pick-up unit, after the QCM (Quartz Crystal Microbalance) stable reading, read the quality of gas to be detected in the gas sample, and gas concentration to be detected in the Calculation of Gas.
Aforesaid a kind of gas sensor based on bacteria cellulose, described 10-1000mg bacteria cellulose film are that 10-1000mg bacteria cellulose dry film or 10-1000mg bacteria cellulose powder or dry weight are the bacterial cellulose wet-coating of 10-1000mg.
Aforesaid a kind of gas sensor based on bacteria cellulose, the described QCM (Quartz Crystal Microbalance) pole drying method that deposits bacteria cellulose fibre comprise 30-100 ℃ of lower dry 1-10h or freeze drying 20-30h.
Aforesaid a kind of gas sensor based on bacteria cellulose, described sensing material are one or more the potpourri in polyethyleneimine, polyvinylamine, polyaniline, poly-diphenylamine, polyortho methylaniline, urea, shitosan, collagen, propionic acid acid amides, triethanolamine, polyacrylamide, polyacrylic acid, polyesteramide, oxalylurea, PDDA, Hydrin, polypropylene-base amine hydrochlorate, the camphorsulfonic acid.
Aforesaid a kind of gas sensor based on bacteria cellulose, described gas to be detected are a kind of in gaseous aldehyde, organic amine gas and the alcohols gases such as ammonia, sulfuretted hydrogen, sulphuric dioxide, sulfuric anhydride, chlorine, formaldehyde.
Beneficial effect
The present invention adopts has the cancellated bacteria cellulose material of 3 D stereo, and it has superhigh specific surface area, by it being deposited on the QCM (Quartz Crystal Microbalance) electrode, can improve largely the sensitivity that detects gas, and detection limit can reach 30ppb.The present invention has that cost is low, highly sensitive, reusable, and long-time stability and selectivity are good, and preparation technology is simple, realizes easily mass production, has solved the deficiency of at present existing gas detection method.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1:
(1) at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and dry up for subsequent use with nitrogen.
500mg bacteria cellulose dry film is immersed in the 500mL distilled water, and at room temperature obtain homodisperse bacteria cellulose aqueous mixtures with hollander with rotating speed 12000r/min making beating 10min.
(2) with micro-pipette the bacteria cellulose aqueous mixtures in the 25 μ L steps (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), freeze drying 24h obtains depositing the QCM (Quartz Crystal Microbalance) electrode of bacteria cellulose fibre.
(3) massfraction 1.0wt% polyethyleneimine: amine aqueous solution 50 μ L are dripped be coated onto on the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose fibre, in 25 ℃ of lower dry 24h.
(4) combination electrode that obtains is placed pick-up unit, by syringe injected gas sample 0.4 μ L in the pick-up unit, after the QCM (Quartz Crystal Microbalance) stable reading, read the quality 1.2 * 10 of formaldehyde in the gas sample
-3Ng, concentration of formaldehyde is 30ppb in the Calculation of Gas.
Embodiment 2:
(1) at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and dry for standby.Be that the bacterial cellulose wet-coating of 10mg immerses in the 50mL distilled water with dry weight, and at room temperature obtain homodisperse bacteria cellulose aqueous mixtures with hollander with the rotating speed 5000r/min 20min that pulls an oar.
(2) with micro-pipette the bacteria cellulose aqueous mixtures in the 50 μ L steps (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), freeze drying 20h obtains depositing the QCM (Quartz Crystal Microbalance) electrode of bacteria cellulose fibre.
(3) massfraction 0.5wt% polyacrylamide solution 25 μ L are dripped be coated onto on the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose fibre, in 20 ℃ of lower dry 24h.
(4) combination electrode that obtains is placed pick-up unit, by syringe injected gas sample 0.4 μ L in the pick-up unit, after the QCM (Quartz Crystal Microbalance) stable reading, read the quality 2 * 10 of formaldehyde in the gas sample
-3Ng, concentration of hydrogen sulfide is 50ppb in the Calculation of Gas.
Embodiment 3:
(1) at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and natural drying for subsequent use.Dry weight is that the 500mg bacterial cellulose wet-coating immerses in the 500mL distilled water, and at room temperature obtains homodisperse bacteria cellulose aqueous mixtures with hollander with rotating speed 12000r/min making beating 8min.
(2) with micro-pipette the bacteria cellulose aqueous mixtures in the 25 μ L steps (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), freeze drying 24h obtains depositing the QCM (Quartz Crystal Microbalance) electrode of bacteria cellulose fibre.
(3) massfraction 0.2wt% polyortho methylaniline aqueous solution 100 μ L are dripped be coated onto on the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose fibre, in 25 ℃ of lower dry 12h.
(4) combination electrode that obtains is placed pick-up unit, by syringe injected gas sample 0.4 μ L in the pick-up unit, after the QCM (Quartz Crystal Microbalance) stable reading, read the quality 8 * 10 of formaldehyde in the gas sample
-3Ng, concentration of hydrogen sulfide is 200ppb in the Calculation of Gas.
Embodiment 4:
(1) dries up or oven dry or natural drying for subsequent use at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and with nitrogen.10mg bacteria cellulose dry film is immersed in the 100mL distilled water, and at room temperature obtain homodisperse bacteria cellulose aqueous mixtures with hollander with rotating speed 5000r/min making beating 20min.
(2) with micro-pipette the bacteria cellulose aqueous mixtures in the 50 μ L steps (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), freeze drying 24h obtains depositing the QCM (Quartz Crystal Microbalance) electrode of bacteria cellulose fibre.
(3) massfraction 1.0wt% triethanolamine solution 200 μ L are dripped be coated onto on the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose fibre, in 25 ℃ of lower dry 24h.
(4) combination electrode that obtains is placed pick-up unit, by syringe injected gas sample 0.4 μ L in the pick-up unit, after the QCM (Quartz Crystal Microbalance) stable reading, read the quality 8 * 10 of sulphuric dioxide in the gas sample
-3Ng, sulfur dioxide concentration is 200ppb in the Calculation of Gas.
Embodiment 5:
(1) at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and natural drying for subsequent use.The 1000mg bacteria cellulose powder is immersed in the 1000mL distilled water, and at room temperature obtain homodisperse bacteria cellulose aqueous mixtures with hollander with rotating speed 15000r/min making beating 20min.
(2) with micro-pipette the bacteria cellulose aqueous mixtures in the 10 μ L steps (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), 100 ℃ of lower dry 1h obtain depositing the QCM (Quartz Crystal Microbalance) electrodes of bacteria cellulose fibre.
(3) massfraction 0.1% triethanolamine aqueous solution 2 μ L are dripped be coated onto on the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose fibre, in 30 ℃ of lower dry 12h.
(4) combination electrode that obtains is placed pick-up unit, by syringe injected gas sample 0.4 μ L in the pick-up unit, after the QCM (Quartz Crystal Microbalance) stable reading, read the quality 4 * 10 of phosgene in the gas sample
-3Ng, phosgene concentration is 100ppb in the Calculation of Gas.
Embodiment 6:
(1) dries up or oven dry or natural drying for subsequent use at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and with nitrogen.500mg bacteria cellulose dry film is immersed in the 500mL distilled water, and at room temperature obtain homodisperse bacteria cellulose aqueous mixtures with hollander with rotating speed 12000r/min making beating 10min.
(2) with micro-pipette the bacteria cellulose aqueous mixtures in the 25 μ L steps (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), freeze drying 24h obtains depositing the QCM (Quartz Crystal Microbalance) electrode of bacteria cellulose fibre.
(3) massfraction 2.0wt% polyacrylic acid aqueous solution 50 μ L are dripped be coated onto on the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose fibre, in 25 ℃ of lower dry 24h.
(4) combination electrode that obtains is placed pick-up unit, by syringe injected gas sample 0.4 μ L in the pick-up unit, after the QCM (Quartz Crystal Microbalance) stable reading, read the quality 5.7 * 10 of ammonia in the gas sample
-3Ng, ammonia concentration is 30ppb in the Calculation of Gas.
Embodiment 7:
(1) at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and natural drying for subsequent use.The 1000mg bacteria cellulose powder is immersed in the 1000mL distilled water, and at room temperature obtain homodisperse bacteria cellulose aqueous mixtures with hollander with rotating speed 15000r/min making beating 20min.
(2) with micro-pipette the bacteria cellulose aqueous mixtures in the 10 μ L steps (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), 100 ℃ of lower dry 1h obtain depositing the QCM (Quartz Crystal Microbalance) electrodes of bacteria cellulose fibre.
(3) massfraction 0.1% polyaniline aqueous solution 2 μ L are dripped be coated onto on the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose fibre, in 30 ℃ of lower dry 12h.
(4) combination electrode that obtains is placed pick-up unit, by syringe injected gas sample 0.4 μ L in the pick-up unit, after the QCM (Quartz Crystal Microbalance) stable reading, read the quality 4 * 10 of formaldehyde in the gas sample
-3Ng, monomethyl amine concentration is 100ppb in the Calculation of Gas.
Embodiment 8:
(1) dries up or oven dry or natural drying for subsequent use at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and with nitrogen.10mg bacteria cellulose dry film is immersed in the 100mL distilled water, and at room temperature obtain homodisperse bacteria cellulose aqueous mixtures with hollander with rotating speed 5000r/min making beating 20min.
(2) with micro-pipette the bacteria cellulose aqueous mixtures in the 50 μ L steps (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), freeze drying 24h obtains depositing the QCM (Quartz Crystal Microbalance) electrode of bacteria cellulose fibre.
(3) massfraction 2.0wt% camphorsulfonic acid aqueous solution 200 μ L are dripped be coated onto on the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose fibre, in 25 ℃ of lower dry 24h.
(4) combination electrode that obtains is placed pick-up unit, by syringe injected gas sample 0.4 μ L in the pick-up unit, after the QCM (Quartz Crystal Microbalance) stable reading, read the quality 8 * 10 of formaldehyde in the gas sample
-3Ng, the first and second determining alcohols are 200ppb in the Calculation of Gas.
Embodiment 9:
(5) at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and natural drying for subsequent use.The 1000mg bacteria cellulose powder is immersed in the 1000mL distilled water, and at room temperature obtain homodisperse bacteria cellulose aqueous mixtures with hollander with rotating speed 15000r/min making beating 20min.
(6) with micro-pipette the bacteria cellulose aqueous mixtures in the 10 μ L steps (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), 100 ℃ of lower dry 1h obtain depositing the QCM (Quartz Crystal Microbalance) electrodes of bacteria cellulose fibre.
(7) massfraction 0.1% polyaniline aqueous solution 2 μ L are dripped be coated onto on the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose fibre, in 30 ℃ of lower dry 12h.
(8) combination electrode that obtains is placed pick-up unit, by syringe injected gas sample 0.4 μ L in the pick-up unit, after the QCM (Quartz Crystal Microbalance) stable reading, read the quality 4 * 10 of formaldehyde in the gas sample
-3Ng, concentration of formaldehyde is 100ppb in the Calculation of Gas.
Embodiment 10:
(1) at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and dry up for subsequent use with nitrogen.300mg bacteria cellulose dry film is immersed in the 300mL distilled water, and at room temperature obtain homodisperse bacteria cellulose aqueous mixtures with hollander with rotating speed 8000r/min making beating 10min.
(2) with micro-pipette the bacteria cellulose aqueous mixtures in the 15 μ L steps (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), freeze drying 25h obtains depositing the QCM (Quartz Crystal Microbalance) electrode of bacteria cellulose fibre.
(3) the poly-diphenylamine aqueous solution 100 μ L of massfraction 0.2wt% are dripped be coated onto on the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose fibre, in 25 ℃ of lower dry 20h.
(4) combination electrode that obtains is placed pick-up unit, by syringe injected gas sample 0.4 μ L in the pick-up unit, after the QCM (Quartz Crystal Microbalance) stable reading, read the quality 8 * 10 of formaldehyde in the gas sample
-3Ng, concentration of formaldehyde is 200ppb in the Calculation of Gas.
Embodiment 11:
(1) at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and dry for standby.Be that the 800mg bacterial cellulose wet-coating immerses in the 800mL distilled water with dry weight, and at room temperature obtain homodisperse bacteria cellulose aqueous mixtures with hollander with the rotating speed 14000r/min 16min that pulls an oar.
(2) with micro-pipette the bacteria cellulose aqueous mixtures in the 10 μ L steps (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), freeze drying 30h obtains depositing the QCM (Quartz Crystal Microbalance) electrode of bacteria cellulose fibre.
(3) the water-soluble drop of massfraction 0.05wt% polyesteramide 200 μ L is coated onto on the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose fibre, in 20 ℃ of lower dry 18h.
(4) combination electrode that obtains is placed pick-up unit, by syringe injected gas sample 0.4 μ L in the pick-up unit, after the QCM (Quartz Crystal Microbalance) stable reading, read the quality 12 * 10 of formaldehyde in the gas sample
-3Ng, concentration of formaldehyde is 300ppb in the Calculation of Gas.
Embodiment 12:
(1) at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and dry up for subsequent use with nitrogen.200mg bacteria cellulose dry film is immersed in the 500mL distilled water, and at room temperature obtain homodisperse bacteria cellulose aqueous mixtures with hollander with rotating speed 10000r/min making beating 15min.
(2) with micro-pipette the bacteria cellulose aqueous mixtures in the 25 μ L steps (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), 30 ℃ of lower dry 10h obtain depositing the QCM (Quartz Crystal Microbalance) electrodes of bacteria cellulose fibre.
(3) massfraction 1.5wt% propionic acid amide aqueous solution 100 μ L are dripped be coated onto on the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose fibre, in 30 ℃ of lower dry 6h.
(4) combination electrode that obtains is placed pick-up unit, by syringe injected gas sample 0.4 μ L in the pick-up unit, after the QCM (Quartz Crystal Microbalance) stable reading, read the quality 32 * 10 of formaldehyde in the gas sample
-3Ng, concentration of formaldehyde is 800ppb in the Calculation of Gas.
Embodiment 13:
(1) at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and dry for standby.Be that the 200mg bacterial cellulose wet-coating immerses in the 500mL distilled water with dry weight, and at room temperature obtain homodisperse bacteria cellulose aqueous mixtures with hollander with the rotating speed 10000r/min 10min that pulls an oar.
(2) with micro-pipette the bacteria cellulose aqueous mixtures in the 30 μ L steps (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), freeze drying 24h obtains depositing the QCM (Quartz Crystal Microbalance) electrode of bacteria cellulose fibre.
(3) massfraction 3wt% aqueous solution of urea 10 μ L are dripped be coated onto on the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose fibre, in 30 ℃ of lower dry 6h.
(4) combination electrode that obtains is placed pick-up unit, by syringe injected gas sample 0.4 μ L in the pick-up unit, after the QCM (Quartz Crystal Microbalance) stable reading, read the quality 16 * 10 of formaldehyde in the gas sample
-3Ng, concentration of formaldehyde is 400ppb in the Calculation of Gas.
Embodiment 14:
(1) at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and dry up for subsequent use with nitrogen.Be that the 100mg bacterial cellulose wet-coating immerses in the 300mL distilled water with dry weight, and at room temperature obtain homodisperse bacteria cellulose aqueous mixtures with hollander with the rotating speed 8000r/min 10min that pulls an oar.
(2) with micro-pipette the bacteria cellulose aqueous mixtures in the 25 μ L steps (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), freeze drying 30h obtains depositing the QCM (Quartz Crystal Microbalance) electrode of bacteria cellulose fibre.
(3) massfraction 3wt% oxalylurea aqueous solution 50 μ L are dripped be coated onto on the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose fibre, in 20 ℃ of lower dry 24h.
(4) combination electrode that obtains is placed pick-up unit, by syringe injected gas sample 0.4 μ L in the pick-up unit, after the QCM (Quartz Crystal Microbalance) stable reading, read the quality 20 * 10 of formaldehyde in the gas sample
-3Ng, concentration of formaldehyde is 500ppb in the Calculation of Gas.
Embodiment 15:
(1) at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and dry up for subsequent use with nitrogen.
The 500mg bacteria cellulose powder is immersed in the 500mL distilled water, and at room temperature obtain homodisperse bacteria cellulose aqueous mixtures with hollander with rotating speed 15000r/min making beating 5min.
(2) with micro-pipette the bacteria cellulose aqueous mixtures in the 10 μ L steps (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), freeze drying 24h obtains depositing the QCM (Quartz Crystal Microbalance) electrode of bacteria cellulose fibre.
(3) massfraction 1.5wt% triethanolamine aqueous solution 50 μ L are dripped be coated onto on the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose fibre, in 25 ℃ of lower dry 24h.
(4) combination electrode that obtains is placed pick-up unit, by syringe injected gas sample 0.4 μ L in the pick-up unit, after the QCM (Quartz Crystal Microbalance) stable reading, read the quality 8 * 10 of formaldehyde in the gas sample
-3Ng, concentration of formaldehyde is 200ppb in the Calculation of Gas.
Embodiment 16:
(1) dries up or oven dry or natural drying for subsequent use at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and with nitrogen.Be that the 500mg bacterial cellulose wet-coating immerses in the 500mL distilled water with dry weight, and at room temperature obtain homodisperse bacteria cellulose aqueous mixtures with hollander with the rotating speed 12000r/min 10min that pulls an oar.
(2) with micro-pipette the bacteria cellulose aqueous mixtures in the 20 μ L steps (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), freeze drying 24h obtains depositing the QCM (Quartz Crystal Microbalance) electrode of bacteria cellulose fibre.
(3) massfraction 2.0wt% collagenic aqueous solution 100 μ L are dripped be coated onto on the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose fibre, in 30 ℃ of lower dry 10h.
(4) combination electrode that obtains is placed pick-up unit, by syringe injected gas sample 0.4 μ L in the pick-up unit, after the QCM (Quartz Crystal Microbalance) stable reading, read the quality 40 * 10 of formaldehyde in the gas sample
-3Ng, concentration of formaldehyde is 1ppm in the Calculation of Gas.
Embodiment 17:
(1) dries up or oven dry or natural drying for subsequent use at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and with nitrogen.Be that the 50mg bacterial cellulose wet-coating immerses in the 500mL distilled water with dry weight, and at room temperature obtain homodisperse bacteria cellulose aqueous mixtures with hollander with the rotating speed 8000r/min 20min that pulls an oar.
(2) with micro-pipette the bacteria cellulose aqueous mixtures in the 50 μ L steps (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), freeze drying 24h obtains depositing the QCM (Quartz Crystal Microbalance) electrode of bacteria cellulose fibre.
(3) massfraction 0.1wt% chitosan aqueous solution 100 μ L are dripped be coated onto on the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose fibre, in 25 ℃ of lower dry 24h.
(4) combination electrode that obtains is placed pick-up unit, by syringe injected gas sample 0.4 μ L in the pick-up unit, after the QCM (Quartz Crystal Microbalance) stable reading, read the quality 40 * 10 of formaldehyde in the gas sample
-3Ng, concentration of formaldehyde is 1ppm in the Calculation of Gas.
Embodiment 18:
(1) dries up or oven dry or natural drying for subsequent use at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and with nitrogen.Be that the 300mg bacterial cellulose wet-coating immerses in the 1000mL distilled water with dry weight, and at room temperature obtain homodisperse bacteria cellulose aqueous mixtures with hollander with the rotating speed 8000r/min 15min that pulls an oar.
(2) with micro-pipette the bacteria cellulose aqueous mixtures in the 25 μ L steps (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), freeze drying 24h obtains depositing the QCM (Quartz Crystal Microbalance) electrode of bacteria cellulose fibre.
(3) massfraction 2.0wt% PDDA aqueous solution 50 μ L are dripped be coated onto on the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose fibre, in 20 ℃ of lower dry 24h.
(4) combination electrode that obtains is placed pick-up unit, by syringe injected gas sample 0.4 μ L in the pick-up unit, after the QCM (Quartz Crystal Microbalance) stable reading, read the quality 2.4 * 10 of formaldehyde in the gas sample
-3Ng, concentration of formaldehyde is 60ppb in the Calculation of Gas.
Embodiment 19:
(1) dries up or oven dry or natural drying for subsequent use at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and with nitrogen.Be that the 500mg bacterial cellulose wet-coating immerses in the 500mL distilled water with dry weight, and at room temperature obtain homodisperse bacteria cellulose aqueous mixtures with hollander with the rotating speed 10000r/min 10min that pulls an oar.
(2) with micro-pipette the bacteria cellulose aqueous mixtures in the 30 μ L steps (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), freeze drying 24h obtains depositing the QCM (Quartz Crystal Microbalance) electrode of bacteria cellulose fibre.
(3) massfraction 1.5wt% polypropylene-base amine hydrochlorate aqueous solution 50 μ L are dripped be coated onto on the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose fibre, in 30 ℃ of lower dry 12h.
(4) combination electrode that obtains is placed pick-up unit, by syringe injected gas sample 0.4 μ L in the pick-up unit, after the QCM (Quartz Crystal Microbalance) stable reading, read the quality 3.2 * 10 of formaldehyde in the gas sample
-3Ng, concentration of formaldehyde is 80ppb in the Calculation of Gas.
Embodiment 20:
(1) dries up or oven dry or natural drying for subsequent use at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and with nitrogen.10mg bacteria cellulose dry film is immersed in the 100mL distilled water, and at room temperature obtain homodisperse bacteria cellulose aqueous mixtures with hollander with rotating speed 5000r/min making beating 20min.
(2) with micro-pipette the bacteria cellulose aqueous mixtures in the 50 μ L steps (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), freeze drying 24h obtains depositing the QCM (Quartz Crystal Microbalance) electrode of bacteria cellulose fibre.
(3) massfraction 2.0wt% polyortho methylaniline aqueous solution 200 μ L are dripped be coated onto on the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose fibre, in 25 ℃ of lower dry 24h.
(4) combination electrode that obtains is placed pick-up unit, by syringe injected gas sample 0.4 μ L in the pick-up unit, after the QCM (Quartz Crystal Microbalance) stable reading, read the quality 8 * 10 of formaldehyde in the gas sample
-3Ng, concentration of formaldehyde is 200ppb in the Calculation of Gas.
Embodiment 21:
(1) dries up or oven dry or natural drying for subsequent use at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and with nitrogen.10mg bacteria cellulose dry film is immersed in the 100mL distilled water, and at room temperature obtain homodisperse bacteria cellulose aqueous mixtures with hollander with rotating speed 5000r/min making beating 20min.
(2) with micro-pipette the bacteria cellulose aqueous mixtures in the 50 μ L steps (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), freeze drying 24h obtains depositing the QCM (Quartz Crystal Microbalance) electrode of bacteria cellulose fibre.
(3) massfraction 2.0wt% Hydrin aqueous solution 200 μ L are dripped be coated onto on the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose fibre, in 25 ℃ of lower dry 24h.
(4) combination electrode that obtains is placed pick-up unit, by syringe injected gas sample 0.4 μ L in the pick-up unit, after the QCM (Quartz Crystal Microbalance) stable reading, read the quality 8 * 10 of formaldehyde in the gas sample
-3Ng, methanol concentration is 200ppb in the Calculation of Gas.
Claims (7)
1. the manufacture method based on the gas sensor of bacteria cellulose is characterized in that comprising the steps:
(1) dries up or oven dry or natural drying for subsequent use at room temperature respectively with the electrode of ethanol and washed with de-ionized water QCM (Quartz Crystal Microbalance), and with nitrogen; Be that the bacteria cellulose of 1:1～5 and distilled water mix with mass volume ratio, and at room temperature homogenous disperse obtain homodisperse bacteria cellulose aqueous mixtures;
(2) with micro-pipette the bacteria cellulose aqueous mixtures in the 10-50 μ L step (1) is dripped and be coated with the electrode surface that is dispersed in QCM (Quartz Crystal Microbalance), drying obtains depositing the QCM (Quartz Crystal Microbalance) electrode of bacteria cellulose fibre;
(3) massfraction 0.05-3wt% sensing material water solution 2-200 μ L is dripped be coated onto on the QCM (Quartz Crystal Microbalance) electrode that deposits bacteria cellulose fibre, in 20-30 ℃ of lower dry 12-24h, namely obtain the gas sensor based on bacteria cellulose.
2. the manufacture method of a kind of gas sensor based on bacteria cellulose as claimed in claim 1 is characterized in that described bacteria cellulose is bacteria cellulose dry film, bacteria cellulose powder or bacterial cellulose wet-coating.
3. the manufacture method of a kind of gas sensor based on bacteria cellulose as claimed in claim 1 is characterized in that, described drying refers to 30-100 ℃ of lower dry 1-10h or freeze drying 20-30h.
4. the manufacture method of a kind of gas sensor based on bacteria cellulose as claimed in claim 1, it is characterized in that described sensing material is one or more the potpourri in polyethyleneimine, polyvinylamine, polyaniline, poly-diphenylamine, polyortho methylaniline, urea, shitosan, collagen, propionic acid acid amides, triethanolamine, polyacrylamide, polyacrylic acid, polyesteramide, oxalylurea, PDDA, Hydrin, polypropylene-base amine hydrochlorate and the camphorsulfonic acid.
5. the manufacture method of a combination electrode is characterized in that comprising the steps:
(1) dries up or oven dry or natural drying for subsequent use at room temperature respectively with ethanol and washed with de-ionized water quartz crystal microelectrode, and with nitrogen; Be that the bacteria cellulose of 1:1～5 and distilled water mix with mass volume ratio, and at room temperature homogenous disperse obtain homodisperse bacteria cellulose aqueous mixtures; (2) the bacteria cellulose aqueous mixtures in the 10-50 μ L step (1) is dripped to be coated be dispersed in electrode surface, drying obtains depositing the combination electrode of bacteria cellulose fibre.
6. the manufacture method of a kind of combination electrode as claimed in claim 5 is characterized in that, described bacteria cellulose is bacteria cellulose dry film, bacteria cellulose powder or bacterial cellulose wet-coating.
7. the manufacture method of a kind of combination electrode as claimed in claim 5 is characterized in that, described drying refers to 30-100 ℃ of lower dry 1-10h or freeze drying 20-30h.
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| CN103033538B (en) * | 2012-12-20 | 2015-01-21 | 中国科学院微电子研究所 | Preparation method for flexible substrate-based sensitive film for detecting gas at normal temperature |
| CN103032790A (en) * | 2012-12-27 | 2013-04-10 | 苏州久三智能科技有限公司 | Ceiling lamp capable of detecting air quality |
| CN103257211B (en) * | 2013-05-31 | 2015-03-25 | 上海大学 | Formaldehyde sensor with sulfobenzide-based chain complex of copper as sensitive material |
| CN104181068B (en) * | 2014-07-21 | 2016-06-01 | 中国科学院理化技术研究所 | Hydrogen cyanide gas and water vapour are had the quartz crystal microbalance sensor that the cupric oxide of contrary response signal is modified |
| CN107498939B (en) * | 2017-07-10 | 2019-07-23 | 东华大学 | One kind is breathed freely high-elastic type single electrode friction nanometer power generator and preparation method thereof |
| CN107970478A (en) * | 2017-11-11 | 2018-05-01 | 丁玉琴 | A kind of solid air freshening agent |
| TWI736133B (en) * | 2020-02-14 | 2021-08-11 | 國立陽明交通大學 | Gas sensor |
| CN114166681A (en) * | 2021-11-12 | 2022-03-11 | 常州大学 | QCM humidity sensor based on high polymer/inorganic composite sensitive material and preparation method thereof |
| CN114441408B (en) * | 2022-01-24 | 2024-05-28 | 蜂巢能源科技(无锡)有限公司 | Method for monitoring fibrosis degree in dry-method film forming process, dry-method film forming method, preparation method of dry-method electrode slice and application |
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| CN101398399A (en) * | 2007-09-26 | 2009-04-01 | 中国科学院大连化学物理研究所 | Quartz crystal resonator, preparation and application thereof |
| CN101865874A (en) * | 2010-06-11 | 2010-10-20 | 东华大学 | High-sensitivity biological sensor and preparation method thereof |
| CN101871873A (en) * | 2010-06-11 | 2010-10-27 | 东华大学 | Heavy metal ion detection device and preparation method thereof |
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| CN101398399A (en) * | 2007-09-26 | 2009-04-01 | 中国科学院大连化学物理研究所 | Quartz crystal resonator, preparation and application thereof |
| CN101865874A (en) * | 2010-06-11 | 2010-10-20 | 东华大学 | High-sensitivity biological sensor and preparation method thereof |
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