CN101871873B - Heavy metal ion detection device and preparation method thereof - Google Patents
Heavy metal ion detection device and preparation method thereof Download PDFInfo
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- CN101871873B CN101871873B CN2010101978719A CN201010197871A CN101871873B CN 101871873 B CN101871873 B CN 101871873B CN 2010101978719 A CN2010101978719 A CN 2010101978719A CN 201010197871 A CN201010197871 A CN 201010197871A CN 101871873 B CN101871873 B CN 101871873B
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Abstract
The invention provides a heavy metal detection device and a preparation method thereof. The device comprises a quartz crystal microbalance, and is characterized in that: polymer fibers are deposited on the electrode of the quartz crystal microbalance; a metal film is sprayed on the polymer fibers; and a sensing material is covered on the metal film. The preparation method is characterized by comprising the following steps: dissolving a spinning polymer raw material in a solvent to obtain an electrospinning material; performing electrostatic spinning by using the electrospinning material; depositing the fibers onto the electrode of the quartz crystal microbalance; spraying the metal film on the fibers; and placing the electrode of the quartz crystal microbalance in a container containing solution of the sensing material for soaking, and taking the electrode out to obtain the heavy metal ion detection device. The device has the advantages of high sensitivity and accurate and quantitative detection.
Description
Technical field
The present invention relates to heavy metal detection device and preparation method thereof, belong to the metal ion detection field.
Background technology
Traditional heavy metal ion detection method such as atomic absorption spectroscopy, inductively coupled plasma emission spectrometry etc. need be carried out pre-service to sample; Testing process is loaded down with trivial details; Must carry out in concentrated the indoor of large-sized analytic instrument; Can't be used for on-the-spot the detection, and detection time is long, is difficult to adapt to actual demand.The heavy metal ion immunodetection that occurred in recent years, though overcome the shortcoming of above-mentioned traditional detection method to a certain extent, immunodetection can only qualitative detection, and can not detection by quantitative.It is research platform with the QCM that external experts and scholars are arranged, and the form of sensitive material with solid membrane covered on the electrode, and the preparation sensor is used for detecting heavy metal ion, but can't overcome the low shortcoming of sensitivity.Human beings'health in the heavy metal ion serious threat, and its pollution problem has become the common problem of paying close attention in various countries, the world today.
Summary of the invention
The purpose of this invention is to provide heavy metal detection device and preparation method thereof, solve above-mentioned detection sensitivity low, can not detection by quantitative and problem such as testing process is loaded down with trivial details, detection time is long.
In order to achieve the above object, technical scheme of the present invention provides a heavy metal detection device, comprises QCM; It is characterized in that; Deposit macromolecular fibre on the electrode of QCM, sprayed metal film on the macromolecular fibre, cover sensing material on the metal film.
The present invention also provides the preparation method of above-mentioned heavy metal ion detection device, it is characterized in that, concrete steps are:
The first step: at room temperature, use magnetic stirring apparatus in solvent, to obtain massfraction the spinning macromolecule raw material and spin raw material as the electricity of 5-30% with the rotating speed stirring and dissolving of 50-2500rpm/min;
Second step: at room temperature, humidity range is under the condition of 40-60%, and the electricity that the first step is obtained spins raw material and is input on the spinning head with the flow velocity of 0.1-10mL/h, simultaneously spinning head is connected the 10-80kV power supply and carries out electrostatic spinning and prepare fiber;
The 3rd step: to the electrode of QCM, the distance between receiving electrode and the spinning head is 5-30cm with spun fiber laydown of second step;
The 4th goes on foot: deposit on the fiber on the QCM electrode in the 3rd step with the vacuum metal sputter and spray metal film, the time of spraying is 0.1-10min;
The 5th step: the electrode that the 4th step was handled the QCM obtain is put in the container that fills sensing material solution and is soaked 1-40h, promptly obtains heavy metal ion detection device after the taking-up.
Spinning macromolecule raw material in the said first step is preferably polystyrene; Polyethylene imine based; Polymethylmethacrylate; Polyaniline; Polyoxyethylene; Gather diphenylamine; Polyortho methylaniline; Hydrin; Polyisobutylene; Polycaprolactone; Polypyrrole; Polyethylene terephthalate; Polyurethane; PLA; Kynoar; Polyesteramide; Polycarbonate; Polyphenylene oxide; Gather-a-amino acid; Polyphenylene sulfide; The potpourri of one or more in epoxy resin and the polysiloxane; Or one or more the potpourri in chitin, shitosan, glucosan, fibrin, silk-fibroin, agar, collagen, carrageenan, mosanom and the calcium alginate.
Solvent in the said first step is preferably absolute ethyl alcohol, formic acid, tetrahydrofuran, N; The potpourri of one or more in dinethylformamide, DMAC N,N, acetone, chloroform, methylene chloride, methyl alcohol, ether, dimethyl sulfoxide (DMSO), benzene, phenixin, ethylene dichloride, trichloroethanes, vinyl chloride, ethane, sulfolane, pyrimidine, formamide, hexane, chlorobenzene, acetonitrile, toluene, methylcyclohexane, dichloroethylene, xylene, cyclohexane, N-Methyl pyrrolidone, propane, pentane, acetate, methyl phenyl ethers anisole, propyl alcohol, amylalcohol, butyl acetate, three fourth MEEs, cumene, ethyl formate, methyl acetate, methylisobutylketone, methane, propane, isooctane, isopropyl ether, methyl isopropyl ketone, sherwood oil, trichloroacetic acid, trifluoroacetic acid and the pyridine.
Metal film in said the 4th step is preferably platinum film, gold film, silverskin or copper film.
Sensing material in said the 5th step is preferably mercaptan acid, mercapto-amine, lipoic acid, thio-acid, amic acid, mercaptan, thiophene, morpholine, pyridine or melanin.
For detected material that is chosen and sensitive material, the specific surface area of sensing material film is big more, and the sensitivity of its demonstration is high more.The specific surface area of electrostatic spinning nano fiber film exceeds the 1-2 one magnitude than the specific surface area of common solid membrane, so be that the specific surface area of the sensing material film of template also can exceed the 1-2 one magnitude with the electrostatic spinning nano fiber film.The specific surface area of sensing material film is big more, and the adsorbable detected material of institute is many more, thereby detection sensitivity is high more.
The present invention compared with prior art its advantage is following:
(1) heavy metal ion detection device provided by the present invention, detection sensitivity is high, but the detectable concentration limit is low, can detect concentration of heavy metal ion and be low to moderate 1ppb;
(2) detection heavy metal ion detection device provided by the present invention can be to carry out detection by quantitative between the 1ppb-100ppm at concentration of heavy metal ion accurately, promptly can accurately detect the concentration of heavy metal ion;
(3) detection heavy metal ion detection device provided by the present invention, have use equipment simple, cheap, be swift in response, advantage such as easy to carry.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Spinning material macromolecule and solvent in following examples can have been bought at Aladdin, and sensing material can buy at Sigma-aldrich; Magnetic stirring apparatus is the 81-2 type of Shanghai Si Le Instr Ltd.; High-voltage power supply is the DW-P303-1ACD8 type that east, Tianjin civilian high-voltage power supply factory produces; QCM is a U.S. Stamford system.
Embodiment 1
(1) at room temperature; It is 3/1 N at the 18g mass ratio with the rotating speed stirring and dissolving of 50rpm/min that 2g polystyrene (degree of polymerization is 1600) solid is used magnetic stirring apparatus; In the mixed solvent of dinethylformamide and tetrahydrofuran, obtain massfraction and be 10% polystyrene solution;
(2) under room temperature, humidity are 40% condition, being 10% polystyrene solution with massfraction is input on the spinning head with the flow velocity of 4mL/h, simultaneously spinning head is connected the 20kV power supply and carries out electrostatic spinning and prepare fiber;
(3) with spun fiber laydown to the electrode of QCM, the distance between receiving electrode and the spinning head is 15cm;
(4) with the vacuum metal sputter fiber that deposits on the QCM electrode is sprayed the gold film, the time of spraying is 1min;
It is that absolute ethyl alcohol, concentration are to soak 24h in the 3-mercaptopropionic acid solution of 10mM that the electrode that (5) will spray the QCM of fiber and gold film is put solvent into, takes out and promptly obtains heavy metal ion detection device.
During use, system connects with QCM, its electrode is immersed in the liquid to be detected detect copper ion, and sensing range is 1ppb-100ppm.
Embodiment 2
(1) at room temperature, with 3g polyaniline (degree of polymerization is 300) with magnetic stirring apparatus with the rotating speed stirring and dissolving of 250rpm/min at 17g N, in the dinethylformamide, obtain massfraction and be 15% polyaniline solutions;
(2) under room temperature, humidity are 50% condition, being 15% polyaniline solutions with massfraction is input on the spinning head with the flow velocity of 2mL/h, simultaneously spinning head is connected the 18kV power supply and carries out electrostatic spinning and prepare fiber;
(3) with spun fiber laydown to the electrode of QCM, the distance between receiving electrode and the spinning head is 10cm;
(4) with the vacuum metal sputter fiber that deposits on the QCM electrode is sprayed silverskin, the time of spraying is 2min;
The electrode that (5) will spray the QCM of fiber and silverskin is put in the N-acryloyl morpholine and is soaked 2h, takes out promptly to obtain heavy metal ion detection device.
During use, system connects with QCM, its electrode is immersed detect nickel, cobalt, zinc ion in the liquid to be detected, and sensing range is 1ppb-100ppm.
Embodiment 3
(1) at room temperature, with 6g polyethylene imine based (degree of polymerization is 500) with magnetic stirring apparatus with the rotating speed stirring and dissolving of 500rpm/min in the 14g methylene chloride, obtain massfraction and be 30% polyethylene imine based solution;
(2) under room temperature, humidity are 60% condition, being 30% polyethylene imine based solution with massfraction is input on the spinning head with the flow velocity of 6mL/h, simultaneously spinning head is connected the 60kV power supply and carries out electrostatic spinning and prepare fiber;
(3) with spun fiber laydown to the electrode of QCM, the distance between receiving electrode and the spinning head is 30cm;
(4) with the vacuum metal sputter fiber that is deposited on the QCM electrode is sprayed copper film, the time of spraying is 10min;
The electrode that (5) will spray the QCM of fiber and gold film is put in 4-(2-sulfydryl) pyridine and is soaked 30h, promptly obtains heavy metal ion detection device after the taking-up.
During use, system connects with QCM, its electrode is immersed in the liquid to be detected detect chromium ion, and sensing range is 1ppb-100ppm.
Embodiment 4
(1) at room temperature, with 0.5g polymethylmethacrylate (degree of polymerization is 200) with magnetic stirring apparatus with the rotating speed stirring and dissolving of 100rpm/min in the 9.5g chloroform, obtain massfraction and be 5% polymethyl methacrylate solution;
(2) under room temperature, humidity are 40% condition, being 5% polymethylmethacrylate with massfraction is input on the spinning head with the flow velocity of 5mL/h, simultaneously spinning head is connected the 12kV power supply and carries out electrostatic spinning and prepare fiber;
(3) with spun fiber laydown to the electrode of QCM, the distance between receiving electrode and the spinning head is 10cm;
(4) with the vacuum metal sputter fiber that deposits on the QCM electrode is sprayed the platinum film, the time of spraying is 0.5min;
It is that absolute ethyl alcohol, concentration are to soak 40h in the 3-dimercaptosuccinic acid solution of 25mM that the electrode that (5) will spray the QCM of fiber and gold film is put solvent into, promptly obtains heavy metal ion detection device after the taking-up.
During use, system connects with QCM, its electrode is immersed detect plumbous, cadmium ion in the liquid to be detected, and sensing range is 1ppb-100ppm.
Embodiment 5
(1) at room temperature, with 2.5g polyurethane (degree of polymerization is 600) with magnetic stirring apparatus with the rotating speed stirring and dissolving of 600rpm/min at the 7.5g DMAC N,N, obtain massfraction and be 25% polyurethane solutions;
(2) under room temperature, humidity are 50% condition, being 25% polyurethane solutions with massfraction is input on the spinning head with the flow velocity of 0.5mL/h, simultaneously spinning head is connected the 50kV power supply and carries out electrostatic spinning and prepare fiber;
(3) with spun fiber laydown to the electrode of QCM, the distance between receiving electrode and the spinning head is 20cm;
(4) with the vacuum metal sputter fiber that deposits on the QCM electrode is sprayed copper film, the time of spraying is 5min;
The electrode that (5) will spray the QCM of fiber and gold film is put into and is soaked 60h in the polythiophene, promptly obtains heavy metal ion detection device after the taking-up.
During use, (please replenish detection method) connects the QCM system, its electrode immersed detect copper, ferric ion in the liquid to be detected, and sensing range is 1ppb-100ppm.
Embodiment 6
(1) at room temperature, with 2g polyoxyethylene (degree of polymerization is 800) with magnetic stirring apparatus with the rotating speed stirring and dissolving of 800rpm/min in the 8g ether, obtain massfraction and be 20% polyethylene oxide solutions;
(2) under room temperature, humidity are 40% condition, being 20% polyethylene oxide solutions with massfraction is input on the spinning head with the flow velocity of 1mL/h, simultaneously spinning head is connected the 18kV power supply and carries out electrostatic spinning and prepare fiber;
(3) with spun fiber laydown to the electrode of QCM, the distance between receiving electrode and the spinning head is 16cm;
(4) with the vacuum metal sputter fiber that deposits on the QCM electrode is sprayed the gold film, the time of spraying is 2min;
The electrode that (5) will spray the QCM of fiber and gold film is put into and is soaked 24h in the melanin, promptly obtains heavy metal ion detection device after the taking-up.
During use, system connects with QCM, its electrode is immersed detect manganese, chromium, lead ion in the liquid to be detected, and sensing range is 1ppb-100ppm.
Embodiment 7
(1) at room temperature, with 1.2g gather diphenylamine (degree of polymerization is 1000) with magnetic stirring apparatus with the rotating speed stirring and dissolving of 1000rpm/min in the 8.8g DMAC N,N, obtain massfraction and be 12% the diphenylamine solution that gathers;
(2) under room temperature, humidity are 60% condition, be that 12% the diphenylamine solution that gathers is input on the spinning head with the flow velocity of 1.5mL/h with massfraction, simultaneously spinning head is connected the 25kV power supply and carry out electrostatic spinning and prepare fiber;
(3) with spun fiber laydown to the electrode of QCM, the distance between receiving electrode and the spinning head is 18cm;
(4) with the vacuum metal sputter fiber that deposits on the QCM electrode is sprayed copper film, the time of spraying is 3min;
The electrode that (5) will spray the QCM of fiber and gold film is put in the acetamide phosphoric acid and is soaked 24h, promptly obtains heavy metal ion detection device after the taking-up.
During use, system connects with QCM, its electrode is immersed detect cadmium, copper, lead ion in the liquid to be detected, and sensing range is 1ppb-100ppm.
Embodiment 8
(1) at room temperature, with 2.2g polyortho methylaniline (degree of polymerization is 300) with magnetic stirring apparatus with the rotating speed stirring and dissolving of 1100rpm/min in 7.8g acetone, obtain massfraction and be 22% polyortho methylaniline solution;
(2) under room temperature, humidity are 40% condition, being 22% polyortho methylaniline solution with massfraction is input on the spinning head with the flow velocity of 1.8mL/h, simultaneously spinning head is connected the 22kV power supply and carries out electrostatic spinning and prepare fiber;
(3) with spun fiber laydown to the electrode of QCM, the distance between receiving electrode and the spinning head is 17cm;
(4) with the vacuum metal sputter fiber that deposits on the QCM electrode is sprayed silverskin, the time of spraying is 4min;
The electrode that (5) will spray the QCM of fiber and gold film is put into and is soaked 30h in the nitrilotriacetic acid, promptly obtains heavy metal ion detection device after the taking-up.
During use, system connects with QCM, its electrode is immersed in the liquid to be detected detect nickel ion, and sensing range is 1ppb-100ppm.
Embodiment 9
(1) at room temperature, with 1.5g Hydrin (degree of polymerization is 200) with magnetic stirring apparatus with the rotating speed stirring and dissolving of 1200rpm/min in the 8.5g methylene chloride, obtain massfraction and be 15% Hydrin solution;
(2) under room temperature, humidity are 40% condition, being 15% Hydrin solution with massfraction is input on the spinning head with the flow velocity of 2.5mL/h, simultaneously spinning head is connected the 20kV power supply and carries out electrostatic spinning and prepare fiber;
(3) with spun fiber laydown to the electrode of QCM, the distance between receiving electrode and the spinning head is 12cm;
(4) with the vacuum metal sputter fiber that deposits on the QCM electrode is sprayed the platinum film, the time of spraying is 0.8min;
(5) will spray in the electrode dipyridine of QCM of fiber and gold film (itself being exactly liquid) and soak 40h, promptly obtain heavy metal ion detection device after the taking-up.
During use, system connects with QCM, its electrode is immersed detect mercury, cadmium, silver ion in the liquid to be detected, and sensing range is 1ppb-100ppm.
Embodiment 10
(1) at room temperature, with 1.8g polyisobutylene (degree of polymerization is 900) with magnetic stirring apparatus with the rotating speed stirring and dissolving of 1300rpm/min in 8.2g methyl alcohol, obtain massfraction and be 18% polyisobutylene solution;
(2) under room temperature, humidity are 40% condition, being 18% polyisobutylene solution with massfraction is input on the spinning head with the flow velocity of 0.8mL/h, simultaneously spinning head is connected the 20kV power supply and carries out electrostatic spinning and prepare fiber;
(3) with spun fiber laydown to the electrode of QCM, the distance between receiving electrode and the spinning head is 12cm;
(4) with the vacuum metal sputter fiber that deposits on the QCM electrode is sprayed the gold film, the time of spraying is 1.2min;
The electrode that (5) will spray the QCM of fiber and gold film is put into and is soaked 25h in the thiosalicylic acid, promptly obtains heavy metal ion detection device after the taking-up.
During use, system connects with QCM, its electrode is immersed detect silver, copper ion in the liquid to be detected, and sensing range is 1ppb-100ppm.
Embodiment 11
(1) at room temperature, with 0.8g polycaprolactone (degree of polymerization is 1200) with magnetic stirring apparatus with the rotating speed stirring and dissolving of 1400rpm/min in 9.2g benzene, obtain massfraction and be 8% polycaprolactone solution;
(2) under room temperature, humidity are 50% condition, being 8% polycaprolactone solution with massfraction is input on the spinning head with the flow velocity of 1mL/h, simultaneously spinning head is connected the 20kV power supply and carries out electrostatic spinning and prepare fiber;
(3) with spun fiber laydown to the electrode of QCM, the distance between receiving electrode and the spinning head is 10cm;
(4) with the vacuum metal sputter fiber that deposits on the QCM electrode is sprayed silverskin, the time of spraying is 4min;
It is that absolute ethyl alcohol, concentration are 3 of 20mM that the electrode that (5) will spray the QCM of fiber and gold film is put solvent into, soaks 15h in the 3-thio-2 acid, promptly obtains heavy metal ion detection device after the taking-up.
During use, system connects with QCM, its electrode is immersed detect nickel, zinc ion in the liquid to be detected, and sensing range is 1ppb-100ppm.
Embodiment 12
(1) at room temperature, with 1g polypyrrole (degree of polymerization is 500) with magnetic stirring apparatus with the rotating speed stirring and dissolving of 1500rpm/min in 9g benzene phenixin, obtain massfraction and be 8% polypyrrole solution;
(2) under room temperature, humidity are 40% condition, being 10% polypyrrole solution with massfraction is input on the spinning head with the flow velocity of 1.2mL/h, simultaneously spinning head is connected the 15kV power supply and carries out electrostatic spinning and prepare fiber;
(3) with spun fiber laydown to the electrode of QCM, the distance between receiving electrode and the spinning head is 15cm;
(4) with the vacuum metal sputter fiber that deposits on the QCM electrode is sprayed silverskin, the time of spraying is 6min;
The electrode that (5) will spray the QCM of fiber and gold film is put into and is soaked 10h in the lipoic acid, promptly obtains heavy metal ion detection device after the taking-up.
During use, system connects with QCM, its electrode is immersed detect manganese, cobalt ions in the liquid to be detected, and sensing range is 1ppb-100ppm.
Embodiment 13
(1) at room temperature, with 1.2g polyvinyl acetate (degree of polymerization is 260) with magnetic stirring apparatus with the rotating speed stirring and dissolving of 1700rpm/min at 8.8g 1, in the 2-ethylene dichloride, obtain massfraction and be 12% polyvinyl acetate solution;
(2) under room temperature, humidity are 40% condition, being 12% polyvinyl acetate solution with massfraction is input on the spinning head with the flow velocity of 4mL/h, simultaneously spinning head is connected the 30kV power supply and carries out electrostatic spinning and prepare fiber;
(3) with spun fiber laydown to the electrode of QCM, the distance between receiving electrode and the spinning head is 15cm;
(4) with the vacuum metal sputter fiber that deposits on the QCM electrode is sprayed copper film, the time of spraying is 3min;
It is that ethanol, concentration are to soak 5h in the TGA of 15mM that the electrode that (5) will spray the QCM of fiber and gold film is put solvent into, promptly obtains heavy metal ion detection device after the taking-up.
During use, system connects with QCM, its electrode is immersed detect cadmium, chromium ion in the liquid to be detected, and sensing range is 1ppb-100ppm.
Claims (4)
1. a heavy metal detection device; Comprise QCM, it is characterized in that, deposit macromolecular fibre on the electrode of QCM; Sprayed metal film on the macromolecular fibre; Metal film is provided with sensing material, and described metal film is platinum film, gold film, silverskin or copper film, and described sensing material is mercaptan acid, mercapto-amine, lipoic acid, thio-acid, amic acid, mercaptan, thiophene, morpholine, pyridine or melanin.
2. the preparation method of the described heavy metal ion detection device of claim 1 is characterized in that, concrete steps are:
The first step: at room temperature, use magnetic stirring apparatus in solvent, to obtain massfraction the spinning macromolecule raw material and spin raw material as the electricity of 5-30% with the rotating speed stirring and dissolving of 50-2500rpm/min;
Second step: at room temperature, humidity range is under the condition of 40-60%, and the electricity that the first step is obtained spins raw material and is input on the spinning head with the flow velocity of 0.1-10mL/h, simultaneously spinning head is connected the 10-80kV power supply and carries out electrostatic spinning and prepare fiber;
The 3rd step: to the electrode of QCM, the distance between receiving electrode and the spinning head is 5-30em with spun fiber laydown of second step;
The 4th goes on foot: deposit on the fiber on the QCM electrode in the 3rd step with the vacuum metal sputter and spray metal film, the time of spraying is 0.1-10 min;
The 5th step: the electrode that the 4th step was handled the QCM obtain is put in the container that fills sensing material or its solution and is soaked 1-40h, promptly obtains heavy metal ion detection device after the taking-up.
3. preparation method according to claim 2; It is characterized in that the spinning macromolecule raw material in the said first step is polystyrene, polyethylene imine based, polymethylmethacrylate, polyaniline, polyoxyethylene, gather diphenylamine, polyortho methylaniline, Hydrin, polyisobutylene, polycaprolactone, polypyrrole, polyethylene terephthalate, polyurethane, PLA, Kynoar, polyesteramide, polycarbonate, polyphenylene oxide, gather-a-amino acid, one or more the potpourri in polyphenylene sulfide, epoxy resin and the polysiloxane; Or one or more the potpourri in chitin, shitosan, glucosan, fibrin, silk-fibroin, agar, collagen, carrageenan, mosanom and the calcium alginate.
4. preparation method according to claim 2; It is characterized in that; Solvent in the first step is absolute ethyl alcohol, formic acid, tetrahydrofuran, N; The potpourri of one or more in dinethylformamide, DMAC N,N, acetone, chloroform, methylene chloride, methyl alcohol, ether, dimethyl sulfoxide (DMSO), benzene, phenixin, ethylene dichloride, trichloroethanes, sulfolane, pyrimidine, formamide, hexane, chlorobenzene, acetonitrile, toluene, methylcyclohexane, dichloroethylene, xylene, cyclohexane, N-Methyl pyrrolidone, propane, pentane, acetate, methyl phenyl ethers anisole, propyl alcohol, amylalcohol, butyl acetate, three fourth MEEs, cumene, ethyl formate, methyl acetate, methylisobutylketone, isooctane, isopropyl ether, methyl isopropyl ketone, sherwood oil, trichloroacetic acid, trifluoroacetic acid and the pyridine.
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| JP5799559B2 (en) * | 2011-04-12 | 2015-10-28 | セイコーエプソン株式会社 | Detection device |
| CN103674624B (en) * | 2013-12-09 | 2016-08-17 | 东南大学 | The sampling film of heavy metal, sampler and application process thereof in enrichment environment air |
| CN104062253B (en) * | 2014-07-01 | 2016-06-29 | 南京医科大学 | A kind of ion concentration batch detector methods based on compressed sensing principle |
| CN104390901B (en) * | 2014-11-17 | 2016-08-10 | 成都柏森松传感技术有限公司 | The monitoring method of microparticle substrate concentration and system in a kind of air |
| JP6764281B2 (en) | 2016-08-09 | 2020-09-30 | 太陽誘電株式会社 | Gas sensor |
| CN107870136B (en) * | 2016-09-28 | 2020-02-21 | 中石化石油工程技术服务有限公司 | Method for measuring cationic degree of zwitterionic sulfonated phenolic resin |
| CN107328684B (en) * | 2017-06-13 | 2020-05-26 | 常州大学 | High-molecular electrostatic self-assembly sensing material for ion detection and preparation method and application thereof |
| CN110041453A (en) * | 2019-04-17 | 2019-07-23 | 河海大学 | A kind of modified Amberlite XAD-4 resin and its preparation method and application |
| CN112858471B (en) * | 2021-01-07 | 2023-10-24 | 浙江诺水科技发展有限公司 | Quartz crystal microbalance sensor, preparation method and application thereof |
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