CN100561212C - The detection method of hydrogen peroxide - Google Patents
The detection method of hydrogen peroxide Download PDFInfo
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- CN100561212C CN100561212C CNB2007100218213A CN200710021821A CN100561212C CN 100561212 C CN100561212 C CN 100561212C CN B2007100218213 A CNB2007100218213 A CN B2007100218213A CN 200710021821 A CN200710021821 A CN 200710021821A CN 100561212 C CN100561212 C CN 100561212C
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- hydrogen peroxide
- surfactant
- sulfide
- electrode
- deoxidizing
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Abstract
The detection method of hydrogen peroxide, step is: (1), preparation nanoscale iron protosulfide: earlier iron ammonium sulfate is dissolved in the letting nitrogen in and deoxidizing secondary water, the mixed solution that adds sulfide and surfactant again, under ultrasound condition, mix, reaction finishes back centrifuge washing precipitation, vacuum drying promptly obtains nanoscale iron protosulfide sample; Wherein the mol ratio of sulfide and surfactant agent is 1: 1, and dosage of surfactant is 0.014M; (2), detect and prepare: on glass-carbon electrode, drip the suspension and the polymer film that are coated with ferrous sulfide nano particles successively, dry, wear out; (3), the detection of hydrogen peroxide: in electrolytic cell, add hydrogen peroxide continuously, carry out Electrochemical Detection, write down its ampere response, promptly obtain testing result.The present invention replaces HRP to detect hydrogen peroxide with nano level iron protosulfide, because nano material has big specific surface area, thus improved the sensitivity that detects, and reached easy, quick, sensitive, stable purpose.
Description
Technical field
The present invention relates to a kind of novelty, easy, quick, sensitive, stable hydrogen peroxide detection method.
Background technology
Hydrogen peroxide is a kind of very important reactive intermediate in clinical medicine and environmental chemistry, and the detection of its concentration has important Research Significance in fields such as chemical analysis, bioanalysis, medicine, clinical diagnosis, environmental analyses.The method of measuring hydrogen peroxide at present mainly contains polarography, flow injection conductance method, electrical analysis, fluorometry, spectrophotometric method and chemiluminescence etc.Wherein electrical analysis is because simple, fast, sensitivity, inexpensive and used widely.Hydrogen peroxide generally reacts the generation current-responsive by horseradish peroxidase (HRP) catalyzing hydrogen peroxide and detects on electrode, but in general, HRP is difficult in the direct betatopic that gets on the electrode as the identification molecule, usually need between HRP and electrode, use electron mediator to come metastatic electron, and HRP not only price is higher, be not easy long preservation, thereby and easily inactivation cause actively reducing stability decreases.
Summary of the invention
In order to solve the problems referred to above that prior art exists, the purpose of this invention is to provide a kind of easy, quick, sensitive, stable hydrogen peroxide detection method.Because the electric activity center of HRP is Fe
3+/ Fe
2+The present invention considers directly to replace HRP to detect hydrogen peroxide with the compound of iron, but the compound of general iron is not enough to the detection sensitivity of hydrogen peroxide, because nano material has big specific surface area, so improve the sensitivity of detection with the compound of nano-level iron.The present invention replaces HRP to detect hydrogen peroxide with nano level iron protosulfide.
The technical scheme of finishing the foregoing invention task is, the detection method of hydrogen peroxide, and step is as follows:
(1), preparation nanoscale iron protosulfide
Earlier iron ammonium sulfate is dissolved in the letting nitrogen in and deoxidizing secondary water, the mixed solution that adds sulfide and surfactant again, under ultrasound condition, mix, reaction finishes back centrifuge washing precipitation, vacuum drying, promptly obtain nanoscale iron protosulfide sample, wherein the mol ratio of sulfide and surfactant agent is 1: 1, and dosage of surfactant is 0.014M);
Described sulfide is selected from Na
2S or thioacetamide recommend to adopt Na
2S;
Described surfactant is selected from dodecylamine hydrochloride, polyglycol or cetyl trimethyl ammonium bromide, recommends to adopt dodecylamine hydrochloride.
(2), detect preparation
On the good glass-carbon electrode of pre-service, drip suspension and the polymer film that is coated with ferrous sulfide nano particles successively, dry, aging;
Described polymer film is selected from: polyvinyl alcohol (PVA), naphthols, cross-link dextran or objective glycan;
(3), the detection of hydrogen peroxide
In electrolytic cell, add hydrogen peroxide continuously, carry out Electrochemical Detection, write down its ampere response, can obtain testing result.
The scheme of more specifically and more optimizing below the present invention recommends: the concrete operations of each step of detection method of hydrogen peroxide are,
(1), preparation nanoscale iron protosulfide
(NH
4)
2SO
4FeSO
46H
2O (0.39121g 0.04M) adds 25mL letting nitrogen in and deoxidizing secondary water, after the dissolving, add dodecylamine hydrochloride (0.0776g, 0.014M) dissolve fully solution A; Na
2S.9H
2(0.1201g 0.04M), adds water-soluble the separating of 10mL letting nitrogen in and deoxidizing secondary to O, dodecylamine hydrochloride (0.014M) is dissolved in 15mL letting nitrogen in and deoxidizing secondary water again, the ultrasonic then Na that mixes down
2The solution of S and dodecylamine hydrochloride obtains emulsus suspension B.Under ultrasonic, with A, B solution successively adds in the three-neck flask of nitrogen atmosphere protection; reaction takes place immediately, and the solution blackening continues behind the ultrasonic 10min centrifugal; successively with deoxygenation secondary water; logical nitrogen absolute ethyl alcohol, each three washing precipitation, washing process allows sample lack ingress of air as far as possible; at last once with logical nitrogen washing with acetone; centrifugal, topple over clear liquid, vacuum drying to sample splits into powder-like.
(2), detect preparation
Nanoscale iron protosulfide suspension and 3% polyvinyl alcohol (PVA) (volume ratio of second alcohol and water is 1: 1) of preparation 3mg/mL in deionized water, on the good glass-carbon electrode of pre-service, drip the polyvinyl alcohol (PVA) that is coated with 2 μ L nanoscale iron protosulfide suspensions and 2 μ L3% successively, dry, aging;
(3), the detection of hydrogen peroxide
On the CHI660 electrochemical workstation, measure, saturated calomel electrode, platinum electrode and nanoscale iron protosulfide modified glassy carbon electrode are respectively as contrast electrode, to electrode and working electrode, letting nitrogen in and deoxidizing is-add continuously hydrogen peroxide under the 400mV to write down its ampere response in operating voltage.
Hydrogen peroxide detection method provided by the invention, replace HRP to detect hydrogen peroxide with nano level iron protosulfide, because nano material has big specific surface area, so improved the sensitivity that detects, simultaneously, reached easy, quick, sensitive, stable purpose.More particularly, effect of the present invention has:
1. when the network of selecting and mixture are dodecylamine hydrochloride, the nanoscale iron protosulfide for preparing has better stability than the trisodium citrate with reported in literature, has wideer detectability, higher sensitivity, better stability and reappearance based on the hydrogen peroxide biology sensor of this structure.
2. operation does not need to regulate pH, and is convenient, is swift in response, and product electrochemical effect aspect is more effective.
3. testing the range of linearity that records the hydrogen peroxide detection is 0.5～150 μ M, detects and is limited to 5.2 * 10
-8M and to come catalytic substrate to react on electrode to produce current-responsive to detect the result that hydrogen peroxide obtains by HRP suitable, but stability is better, can be used for the detection of concentration of hydrogen peroxide in clinical and the environmental chemistry.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) figure of the used ferrous sulfide nano particles of the present invention;
Fig. 2 is the hydrogen peroxide biology sensor of the present invention's preparation, promptly add 0.10 respectively, 0.20,0.40,0.60and0.70mM hydrogen peroxide (from top to bottom), the cyclic voltammogram of ferrous sulfide nano particles modified glassy carbon electrode is swept speed: 100mV/s, electrolytic solution: the buffer solution of 0.1M pH7.0.
Embodiment
(1), preparation nanoscale iron protosulfide: (NH
4)
2SO
4FeSO
46H
2O (0.39121g) adds 25mL letting nitrogen in and deoxidizing secondary water, after the dissolving, add dodecylamine hydrochloride (0.0776g) dissolve fully solution A; Na
2S.9H
2O (0.1201g) adds water-soluble the separating of 10mL letting nitrogen in and deoxidizing secondary, dodecylamine hydrochloride is dissolved in 15mL letting nitrogen in and deoxidizing secondary water again, obtains the solution of 0.014M; The ultrasonic then Na that mixes down
2S.9H
2The solution of O and dodecylamine hydrochloride obtains emulsus suspension B.Under ultrasonic, with A, B solution successively adds in the three-neck flask of nitrogen atmosphere protection; reaction takes place immediately, and the solution blackening continues behind the ultrasonic 10min centrifugal; successively with deoxygenation secondary water; logical nitrogen absolute ethyl alcohol, each three washing precipitation, washing process allows sample lack ingress of air as far as possible; at last once with logical nitrogen washing with acetone; centrifugal, topple over clear liquid, vacuum drying to sample splits into powder-like.
(2), detect preparation: nanoscale iron protosulfide suspension and 3% polyvinyl alcohol (PVA) (volume ratio of second alcohol and water is 1: 1) of preparation 3mg/mL in deionized water, on the good glass-carbon electrode of pre-service, drip the polyvinyl alcohol (PVA) that is coated with 2 μ L nanoscale iron protosulfide suspensions and 2 μ L3% successively, dry, aging;
(3), the detection of hydrogen peroxide: on CHI 660 electrochemical workstations, measure, saturated calomel electrode, platinum electrode and nanoscale iron protosulfide modified glassy carbon electrode are respectively as contrast electrode, to electrode and working electrode, letting nitrogen in and deoxidizing, in operating voltage be-add continuously hydrogen peroxide under the 400mV, write down its ampere response.
Claims (3)
1, a kind of detection method of hydrogen peroxide, step is as follows:
(1), preparation nanoscale iron protosulfide
Earlier iron ammonium sulfate is dissolved in the letting nitrogen in and deoxidizing secondary water, adds the mixed solution of sulfide and surfactant again, mix under ultrasound condition, reaction finishes back centrifuge washing precipitation, and vacuum drying promptly obtains nanoscale iron protosulfide sample;
Wherein the mol ratio of sulfide and surfactant is 1: 1, and dosage of surfactant is 0.014M;
(2), detect preparation
On the good glass-carbon electrode of pre-service, drip suspension and the polymer film that is coated with ferrous sulfide nano particles successively, dry, aging;
(3), the detection of hydrogen peroxide
In electrolytic cell, add hydrogen peroxide continuously, carry out Electrochemical Detection, write down its ampere response, can obtain testing result;
Described sulfide is selected from Na
2S or thioacetamide;
Described surfactant is selected from dodecylamine hydrochloride, polyglycol or cetyl trimethyl ammonium bromide;
Described polymer film is selected from: polyvinyl alcohol (PVA), naphthols, cross-link dextran or shitosan.
2, according to the detection method of the described hydrogen peroxide of claim 1, it is characterized in that,
Described sulfide adopts Na
2S;
Described surfactant adopts dodecylamine hydrochloride.
According to the detection method of claim 1 or 2 described hydrogen peroxide, it is characterized in that 3, the concrete operations of each step are,
(1), preparation nanoscale iron protosulfide
(NH4)
2SO
4FeSO
46H
2O, 0.39121g adds 25mL letting nitrogen in and deoxidizing secondary water, after the dissolving, adds the 0.0776g dodecylamine hydrochloride, dissolve fully solution A; With 0.1201g Na
2S.9H
2O adds water-soluble the separating of 10mL letting nitrogen in and deoxidizing secondary, dodecylamine hydrochloride is dissolved in 15mL letting nitrogen in and deoxidizing secondary water again, obtains the solution of 0.014M; The ultrasonic then Na that mixes down
2S.9H
2The solution of O and dodecylamine hydrochloride obtains emulsus suspension B; Under ultrasonic, with A, B solution successively adds in the three-neck flask of nitrogen atmosphere protection, reaction takes place immediately, and the solution blackening continues behind the ultrasonic 10min centrifugal, successively with deoxygenation secondary water, logical nitrogen absolute ethyl alcohol, each three washing precipitation, washing process allows sample lack ingress of air as far as possible, at last once with logical nitrogen washing with acetone, centrifugal, topple over clear liquid, vacuum drying to sample splits into powder-like;
(2), detect preparation
Nanoscale iron protosulfide suspension and 3% polyvinyl alcohol (PVA) of preparation 3mg/mL in deionized water, the volume ratio of second alcohol and water is 1: 1, on the good glass-carbon electrode of pre-service, drip the polyvinyl alcohol (PVA) that is coated with 2 μ L nanoscale iron protosulfide suspensions and 2 μ L3% successively, dry, aging;
(3), the detection of hydrogen peroxide
On the CHI660 electrochemical workstation, measure, saturated calomel electrode, platinum electrode and nanoscale iron protosulfide modified glassy carbon electrode be respectively as contrast electrode, to electrode and working electrode, letting nitrogen in and deoxidizing,
In operating voltage be-add continuously hydrogen peroxide under the 400mV, write down its ampere response.
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| CN102520034B (en) * | 2011-12-16 | 2014-01-29 | 江南大学 | Method for electrochemically measuring content of hydroperoxides in emulsion |
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Non-Patent Citations (4)
| Title |
|---|
| 均相沉淀法制备纳米硫化亚铁. 陈凡等.复旦学报（自然科学版），第42卷第3期. 2003 |
| 均相沉淀法制备纳米硫化亚铁. 陈凡等.复旦学报（自然科学版），第42卷第3期. 2003 * |
| 纳米催化剂FeS的制备及其在气相生长碳纤维中的应用. 付铁岩等.材料科学与工程学报，第23卷第5期. 2005 |
| 纳米催化剂FeS的制备及其在气相生长碳纤维中的应用. 付铁岩等.材料科学与工程学报，第23卷第5期. 2005 * |
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