CN105675689A - Preparation method for hydrogen peroxide non-enzymatic sensor established based on molybdenum sulfide composite and application - Google Patents
Preparation method for hydrogen peroxide non-enzymatic sensor established based on molybdenum sulfide composite and application Download PDFInfo
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Abstract
The invention discloses a preparation method for a non-enzymatic difunctional hydrogen peroxide sensor established based on a molybdenum sulfide composite. The prepared sensor is easy to operate, convenient to carry, high in detection speed and low in cost and can be used for rapidly and sensitively detecting hydrogen peroxide in the fields of routine production, life and the like.
Description
Technical field
The preparation method that the present invention relates to a kind of sensor for detecting hydrogen peroxide, this sensor integration electrochemiluminescence and Optical Electro-Chemistry dual-use function. Belong to Nano-function thin films and electrochemical biosensor analysis technical field.
Background technology
Hydrogen peroxide is a kind of oxidant, generally can be decomposed into water and oxygen, but it is slow, when adding catalyst (or enzyme), response speed is accelerated, thus can be made instantly available the amount of hydrogen peroxide or the amount of catalyst (or enzyme), hydrogen peroxide also often exists with the form of reaction intermediate in vivo simultaneously, therefore, hydrogen peroxide all plays important role in fields such as medical diagnosis, clinical treatment, environment measuring and food productions, and research and development hydrogen peroxide detection method also just has highly important using value. Electrochemical biosensor analytical technology, due to easy and simple to handle, the detection advantages such as speed is fast, obtains the attention of people day by day. The electrochemical biosensor analytical technology being presently used for detection hydrogen peroxide is divided according to detection means and is mainly had electrochemical sensor, electrochemical luminous sensor and Optical Electro-Chemistry sensor three kinds. Wherein, electrochemical luminous sensor and Optical Electro-Chemistry sensor, relative to electrochemical sensor, have the features such as background signal noise is few, highly sensitive, testing cost is low, were paid close attention to by increasing researcher in recent years.
Electrochemiluminescence is also referred to as electrochemiluminescence, refer to and produce some special materials by electrochemical method at electrode surface, between these materials or and system in form excited state by electron transmission between other components, excited state return to ground state and produce luminescence phenomenon. Namely electrochemical luminous sensor by changing the decorative material of electrode surface, produces electrochemiluminescence with analyte, in optimal conditions, realizes the qualitative and quantitative analysis to analyte according to the associated change of analyte concentration with electrochemiluminescence intensity.
Optical Electro-Chemistry sensor is based on additional light source activation Electrophotosensitivmaterial material and causes that electron-hole pair is easily separated, under suitable inclined potential condition, it is achieved the electronics quick transmission on electrode, quasiconductor and trim and analyte, and forms photoelectric current. In optimal conditions, the change of analyte concentration can directly affect the size of photoelectric current, it is possible to realizes the qualitative and quantitative analysis to analyte according to the change of photoelectric current.
But, owing to electrochemical luminous sensor needs external optical signal to catch equipment such as photodiode etc., and Optical Electro-Chemistry sensor needs peripheral hardware light source to excite Electrophotosensitivmaterial material, this have impact on the convenience of the two operation to a certain extent, limits them and is more widely applied in actual production, life. Therefore, the electrochemical biosensor analytical technology designing, preparing more simple, fast detection hydrogen peroxide has highly important practical value.
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of simple to operate, easy to carry, detection is fast, cost is low hydrogen peroxide sensor, prepared sensor, can be used for quick, the Sensitive Detection to hydrogen peroxide in the fields such as daily production, life.Based on this purpose, the present invention, in same electrolyzer, adopts four electrode systems, namely two working electrodes, one to electrode and a reference electrode, wherein working electrode 1 adopts the molybdenum bisuphide composite Zn-MoS of zinc doping2Jointly modifying with electropolymerization luminol, as electrochemiluminescence working electrode W1, working electrode 2 adopts reduced graphene carried titanium dioxide nano-film sol rGO/TiO2Jointly modify with chlorhematin Hemin solution, as Optical Electro-Chemistry working electrode W2. When detecting, after adding hydrogen peroxide in electrolyzer, W1 applies step voltage, due to Zn-MoS2Having bigger serface and good electric conductivity can load and stablize the effect of luminol, sufficient luminol and hydroperoxidation, produce electrochemiluminescence, this is just equivalent to " turning on light ", when step voltage is 0, electrochemiluminescence disappears, and this is just equivalent to " turning off the light ", on W2, meanwhile apply constant voltage, due to rGO/TiO always2Can because the luminescence that electrochemiluminescence produces excites causes that electron-hole pair is easily separated, Hemin catalyzing hydrogen peroxide produces oxygen, hydrogen peroxide is made to become hole " donor ", thus obtaining photoelectric current on W2, when electrochemiluminescence disappears, when namely " turning off the light ", photoelectric current disappears immediately, the size of the photoelectric current produced and concentration of hydrogen peroxide positive correlation, therefore can realize the detection to hydrogen peroxide by the size of recording light electric current.
Based on above inventive principle, the concrete technical scheme that the present invention adopts is as follows:
1. the hydrogen peroxide built based on molybdenum sulfide composite is without the preparation method of enzyme sensor, and it is characterized in that, preparation process is:
(1) preparation method of electrochemiluminescence working electrode W1, described W1 is by Zn-MoS2The ITO electro-conductive glass jointly modified with electropolymerization luminol, is characterized in, concrete preparation process is:
1) with ITO electro-conductive glass for working electrode, at electrode surface drop coating Zn-MoS2, area coverage is 1cm × 1cm, dries under room temperature;
2) by 1) working electrode that obtains, immerse in electrolyte, immersion area is Zn-MoS2The area covered, utilizes three-electrode system that working electrode is carried out electrochemical deposition, takes out working electrode after deposition, uses ultra-pure water to clean, and at 4 DEG C, lucifuge dries, and prepares electrochemiluminescence working electrode W1;
Described Zn-MoS2For the molybdenum bisuphide two-dimension nano materials doped with zinc ion, described two-dimension nano materials is scraps of paper shape, and thickness is about 10 ~ 20nm; Described Zn-MoS2Preparation method be: by 0.005 ~ 0.01g zinc chloride ZnCl2, the 0.1mol/L ascorbic acid solution of 2 ~ 6mL, 0.5 ~ 1.5mL sodium molybdate Na2MoO4Solution and 0.01 ~ 0.03g sodium sulfide Na2S, after being mixed and stirred for 15 minutes, puts in reactor, at 150 ~ 220 DEG C, reacts 12 ~ 16 hours; After being cooled to room temperature, use deionized water centrifuge washing, at 40 DEG C, carry out vacuum drying, namely prepare Zn-MoS2, it is dissolved in deionized water and prepares Zn-MoS2Solution;
Described electrolyte is the sulfuric acid solution containing luminol, and in described electrolyte, the concentration of luminol is 1 ~ 10mmol/L, and sulfuric acid concentration is 0.1 ~ 1.0mol/L;
Described three-electrode system, including working electrode, reference electrode and to electrode, described reference electrode is saturated calomel electrode, and described is platinum electrode to electrode;
Described electrochemical deposition process, the electrochemical method of employing is cyclic voltammetry, and starting voltage is-0.2V, and final voltage is 1.5V, sweeps speed for 100mv/s, circulation 20 ~ 30 circle;
(2) preparation method of Optical Electro-Chemistry working electrode W2, described W2 is by rGO/TiO2With the Hemin ITO electro-conductive glass jointly modified, be characterized in, concrete preparation process is:
1) with ITO electro-conductive glass for working electrode, at electrode surface drop coating 8 ~ 12 μ LrGO/TiO2, dry under room temperature;
2) by 1) in the working electrode that obtains put in Muffle furnace, be annealed processing at 450 DEG C, after process, be cooled to room temperature;
3) by 2) in working electrode surface drop coating 8 ~ 12 μ LHemin that obtains, dry at 4 DEG C, clean with ultra-pure water after drying, dry at 4 DEG C, prepare Optical Electro-Chemistry working electrode W2;
Described rGO/TiO2For the aqueous solution of reduced graphene carried titanium dioxide nanometer sheet, described titanium dioxide nanoplate is the titanium dioxide nano-particle of square lamellar, and the length of side is 60 ~ 80nm;
Described Hemin is the chlorhematin aqueous solution of 5 μm of ol/L;
(3) hydrogen peroxide built based on molybdenum sulfide composite is without the preparation method of enzyme sensor:
1) one side that W1 and W2 conducts electricity relatively being inserted in electrolyzer, W1 and W2 spacing is 0.5cm ~ 1.5cm;
2) with Ag/AgCl be reference electrode RE, platinum electrode be to electrode CE, insert in electrolyzer, collectively constitute four electrode systems with W1 and W2;
3) adding 10mLpH value in electrolyzer is the NaOH solution of 11 ~ 13;
4) by 1) ~ 3) obtained by four electrode systems and electrolyzer be placed in magazine, namely prepare the hydrogen peroxide built based on molybdenum sulfide composite without enzyme sensor.
2. the hydrogen peroxide built based on molybdenum sulfide composite of the present invention is without the detection being applied to hydrogen peroxide of enzyme sensor, and the detection method being characterized in concrete is:
(1) utilizing electrochemical workstation, adopt the method for step voltage that W1 applies step voltage on W1, initial voltage is 0v, and step voltage is 0.7 ~ 0.9v, and snap time is 10 ~ 30s; Meanwhile, when adopting on W2, W2 is applied constant voltage by m-current methods, and voltage is 0 ~ 0.6v;
(2) adding the Hydrogen peroxide standard solution of variable concentrations in electrolyzer, the electric current on W2 can increase accordingly along with the increase of concentration of hydrogen peroxide, according to the relation between gained electric current increase value and concentration of hydrogen peroxide, drawing curve;
(3) hydrogenperoxide steam generator to be measured is replaced the standard solution of hydrogen peroxide, hydrogen peroxide detection method described in (1) and (2) detects, and draws the concentration of hydrogenperoxide steam generator to be measured according to obtained electric current increase value and the working curve drawn.
The useful achievement of the present invention
(1) hydrogen peroxide built based on molybdenum sulfide composite of the present invention is simple without enzyme sensor preparation, easy to operate, without external accessory, utilize the microminiaturization of detection equipment, portability, and achieve the selective enumeration method quick, sensitive, high to hydrogen peroxide, there is wide market development prospect;
(2) present invention adopts four electrode system detection hydrogen peroxide first in same electrolyzer, and achieves electrochemiluminescence signal amplification strategy difunctional with Optical Electro-Chemistry. Along with the increase of concentration of hydrogen peroxide in electrolyzer, on the one hand, make electrochemiluminescence intensity linearly increasing, the linear increase of photoelectric current excited; On the other hand, hydrogen peroxide is as electron donor so that the linear increase of photoelectric current in Optical Electro-Chemistry reaction. Therefore, electrochemiluminescence and two kinds of methods of Optical Electro-Chemistry are reaction jointly, interaction in same electrolyzer, under same electrochemical workstation, achieve the dual amplification that hydrogen peroxide is detected the signal of telecommunication, drastically increase detection sensitivity and detection limit, simultaneously because do not use enzyme, thus detection environmental requirement is more loose, there is important scientific meaning and market using value.
Detailed description of the invention
The hydrogen peroxide that embodiment 1 one kinds builds based on molybdenum sulfide composite is without enzyme sensor, and concrete preparation process is:
(1) Zn-MoS2Preparation:
By 0.005g zinc chloride ZnCl2, the 0.1mol/L ascorbic acid solution of 2mL, 0.5mL sodium molybdate Na2MoO4Solution and 0.01g sodium sulfide Na2S, after being mixed and stirred for 15 minutes, puts in reactor, at 150 DEG C, reacts 16 hours;After being cooled to room temperature, use deionized water centrifuge washing, at 40 DEG C, carry out vacuum drying, namely prepare Zn-MoS2, it is dissolved in deionized water and prepares Zn-MoS2Solution.
(2) preparation of electrochemiluminescence working electrode W1:
1) with ITO electro-conductive glass for working electrode, the Zn-MoS of preparation in electrode surface drop coating (1)2Solution, area coverage is 1cm × 1cm, dries under room temperature;
2) by 1) working electrode that obtains, immerse in electrolyte, immersion area is Zn-MoS2The area covered, utilizes three-electrode system that working electrode is carried out electrochemical deposition, takes out working electrode after deposition, uses ultra-pure water to clean, and at 4 DEG C, lucifuge dries, and prepares electrochemiluminescence working electrode W1;
Described electrolyte is the sulfuric acid solution containing luminol, and in described electrolyte, the concentration of luminol is 1mmol/L, and sulfuric acid concentration is 0.1mol/L;
Described three-electrode system, including working electrode, reference electrode and to electrode, described reference electrode is saturated calomel electrode, and described is platinum electrode to electrode;
Described electrochemical deposition process, the electrochemical method of employing is cyclic voltammetry, and starting voltage is-0.2V, and final voltage is 1.5V, sweeps speed for 100mv/s, circulation 20 circle.
(3) preparation of Optical Electro-Chemistry working electrode W2:
1) with ITO electro-conductive glass for working electrode, at electrode surface drop coating 8 μ LrGO/TiO2, dry under room temperature;
2) by 1) in the working electrode that obtains put in Muffle furnace, be annealed processing at 450 DEG C, after process, be cooled to room temperature;
3) by 2) in the working electrode surface drop coating 8 μ LHemin that obtains, dry at 4 DEG C, clean with ultra-pure water after drying, dry at 4 DEG C, prepare Optical Electro-Chemistry working electrode W2;
Described rGO/TiO2For the aqueous solution of reduced graphene carried titanium dioxide nanometer sheet, described titanium dioxide nanoplate is the titanium dioxide nano-particle of square lamellar, and the length of side is 60 ~ 80nm;
Described Hemin is the chlorhematin aqueous solution of 5 μm of ol/L.
(4) hydrogen peroxide built based on molybdenum sulfide composite is without the preparation method of enzyme sensor:
1) being inserted face to face in electrolyzer by the W1 of preparation in (2) and the W2 of (3) middle preparation, W1 and W2 spacing is 0.5cm;
2) with Ag/AgCl be reference electrode RE, platinum electrode be to electrode CE, insert in electrolyzer, collectively constitute four electrode systems with W1 and W2;
3) adding 10mLpH value in electrolyzer is the NaOH solution of 11;
4) by 1) ~ 3) obtained by four electrode systems and electrolyzer be placed in magazine, namely prepare the hydrogen peroxide built based on molybdenum sulfide composite without enzyme sensor.
The hydrogen peroxide that embodiment 2 one kinds builds based on molybdenum sulfide composite is without enzyme sensor, and concrete preparation process is:
(1) Zn-MoS2Preparation:
Preparation process is with Zn-MoS in embodiment 12The preparation method of solution, difference is: ZnCl2Addition be 0.008g, ascorbic acid solution addition be 4mL, Na2MoO4The addition of solution is 1.0mL and Na2The addition of S is 0.02g, at 220 DEG C, reacts 12 hours.
(2) preparation of electrochemiluminescence working electrode W1:
Preparation process is with the preparation process of W1 in embodiment 1, and difference is: use the Zn-MoS obtained by (1) in the present embodiment2Modified electrode; In electrolyte, the concentration of luminol is 5mmol/L, and sulfuric acid concentration is 0.5mol/L, when cyclic voltammetry carries out electrochemical deposition, and circulation 25 circle.
(3) preparation of Optical Electro-Chemistry working electrode W2:
1) with ITO electro-conductive glass for working electrode, at electrode surface drop coating 10 μ LrGO/TiO2, dry under room temperature;
2) by 1) in the working electrode that obtains put in Muffle furnace, be annealed processing at 450 DEG C, after process, be cooled to room temperature;
3) by 2) in the working electrode surface drop coating 10 μ LHemin that obtains, dry at 4 DEG C, clean with ultra-pure water after drying, dry at 4 DEG C, prepare Optical Electro-Chemistry working electrode W2;
All the other are with the preparation process of W2 in embodiment 1.
(4) hydrogen peroxide built based on molybdenum sulfide composite is without the preparation method of enzyme sensor:
Preparation process is with embodiment 1, and difference is W1 and W2 spacing is 1.0cm, and the pH value of the NaOH solution added in electrolyzer is 12.
The hydrogen peroxide that embodiment 3 one kinds builds based on molybdenum sulfide composite is without enzyme sensor, and concrete preparation process is:
(1) Zn-MoS2Preparation:
Preparation process is with Zn-MoS in embodiment 12The preparation method of solution, difference is: ZnCl2Addition be 0.01g, ascorbic acid solution addition be 6mL, Na2MoO4The addition of solution is 1.5mL and Na2The addition of S is 0.03g, at 220 DEG C, reacts 12 hours.
(2) preparation of electrochemiluminescence working electrode W1:
Preparation process is with the preparation process of W1 in embodiment 1, and difference is: use the Zn-MoS obtained by (1) in the present embodiment2Modified electrode; In electrolyte, the concentration of luminol is 10mmol/L, and sulfuric acid concentration is 1.0mol/L, when cyclic voltammetry carries out electrochemical deposition, and circulation 30 circle.
(3) preparation of Optical Electro-Chemistry working electrode W2:
1) with ITO electro-conductive glass for working electrode, at electrode surface drop coating 12 μ LrGO/TiO2, dry under room temperature;
2) by 1) in the working electrode that obtains put in Muffle furnace, be annealed processing at 450 DEG C, after process, be cooled to room temperature;
3) by 2) in the working electrode surface drop coating 12 μ LHemin that obtains, dry at 4 DEG C, clean with ultra-pure water after drying, dry at 4 DEG C, prepare Optical Electro-Chemistry working electrode W2;
All the other are with the preparation process of W2 in embodiment 1.
(4) hydrogen peroxide built based on molybdenum sulfide composite is without the preparation method of enzyme sensor:
Preparation process is with embodiment 1, and difference is W1 and W2 spacing is 1.5cm, and the pH value of the NaOH solution added in electrolyzer is 13.
The hydrogen peroxide that embodiment 4 one kinds builds based on molybdenum sulfide composite is without the application of enzyme sensor
A kind of hydrogen peroxide built based on molybdenum sulfide composite of embodiment 1 preparation is applied to the detection of hydrogen peroxide without enzyme sensor, and its detecting step is:
(1) utilizing electrochemical workstation, adopt the method for step voltage that W1 applies step voltage on W1, initial voltage is 0v, and step voltage is 0.7v, and snap time is 10s; Meanwhile, when adopting on W2, W2 is applied constant voltage by m-current methods, and voltage is 0v;
(2) adding the Hydrogen peroxide standard solution of variable concentrations in electrolyzer, the electric current on W2 can increase accordingly along with the increase of concentration of hydrogen peroxide, according to the relation between gained electric current increase value and concentration of hydrogen peroxide, drawing curve;
(3) hydrogenperoxide steam generator to be measured is replaced the standard solution of hydrogen peroxide, hydrogen peroxide detection method described in (1) and (2) detects, and draws the concentration of hydrogenperoxide steam generator to be measured according to obtained electric current increase value and the working curve drawn.
The hydrogen peroxide that embodiment 5 one kinds builds based on molybdenum sulfide composite is without the application of enzyme sensor
A kind of hydrogen peroxide built based on molybdenum sulfide composite of embodiment 2 preparation is applied to the detection of hydrogen peroxide without enzyme sensor, and its detecting step is:
(1) utilizing electrochemical workstation, adopt the method for step voltage that W1 applies step voltage on W1, initial voltage is 0v, and step voltage is 0.8v, and snap time is 20s; Meanwhile, when adopting on W2, W2 is applied constant voltage by m-current methods, and voltage is 0.3v;
(2) and (3) with embodiment 4.
The hydrogen peroxide that embodiment 6 one kinds builds based on molybdenum sulfide composite is without the application of enzyme sensor
A kind of hydrogen peroxide built based on molybdenum sulfide composite of embodiment 3 preparation is applied to the detection of hydrogen peroxide without enzyme sensor, and its detecting step is:
(1) utilizing electrochemical workstation, adopt the method for step voltage that W1 applies step voltage on W1, initial voltage is 0v, and step voltage is 0.9v, and snap time is 30s; Meanwhile, when adopting on W2, W2 is applied constant voltage by m-current methods, and voltage is 0.6v;
(2) and (3) with embodiment 4.
The hydrogen peroxide based on molybdenum sulfide composite structure prepared by embodiment 7 embodiment 1-3, without enzyme sensor, is applied to the detection of hydrogen peroxide, has excellent Detection results, and detection is limited to 8 μm of ol/L.
The detection of hydrogen peroxide in embodiment 8 human serum
Accurately pipette human serum sample, add the Hydrogen peroxide standard solution of certain molar concentration, with do not add hydrogen peroxide human serum for blank, carry out recovery testu, detecting according to the step of embodiment 4 ~ 6, measure the response rate of hydrogen peroxide in sample, testing result is in Table 1.
The testing result of hydrogen peroxide in table 1 human serum
Table 1 testing result is it can be seen that the relative standard deviation (RSD) of result is not more than 3.0%, and the response rate is 94 ~ 106%, it was shown that the present invention can be used for the detection of hydrogen peroxide in human serum, and highly sensitive, the high specificity of method, result is accurately and reliably.
Claims (5)
1. the hydrogen peroxide built based on molybdenum sulfide composite is without the preparation method of enzyme sensor, it is characterised in that adopt the molybdenum bisuphide composite Zn-MoS of zinc doping2The ITO electro-conductive glass jointly modified with electropolymerization luminol is as electrochemiluminescence working electrode W1, reduced graphene carried titanium dioxide nano-film sol rGO/TiO2The ITO electro-conductive glass jointly modified with chlorhematin Hemin solution is as Optical Electro-Chemistry working electrode W2, Ag/AgCl electrode as reference electrode RE, platinum electrode as to electrode CE, four electrodes are inserted jointly same electrolyzer forms four electrode systems, four prepared electrode systems are placed in magazine, namely prepare the hydrogen peroxide based on molybdenum sulfide composite structure without enzyme sensor.
2. preparation method according to claim 1, it is characterised in that the molybdenum bisuphide composite Zn-MoS of described zinc doping2For the molybdenum bisuphide two-dimension nano materials doped with zinc ion, described two-dimension nano materials is scraps of paper shape, and thickness is about 10 ~ 20nm.
3. preparation method according to claim 1, it is characterised in that described reduced graphene carried titanium dioxide nano-film sol rGO/TiO2For the aqueous solution of reduced graphene carried titanium dioxide nanometer sheet, described titanium dioxide nanoplate is the titanium dioxide nano-particle of square lamellar, and the length of side is 60 ~ 80nm.
4. preparation method according to claim 1, it is characterised in that the one side that W1 and W2 conducts electricity relatively being inserted in electrolyzer, W1 and W2 spacing is 0.5cm ~ 1.5cm.
5. the hydrogen peroxide that prepared by preparation method according to claim 1 is without enzyme sensor, it is characterized in that, the step that described hydrogen peroxide is applied to hydrogen peroxide detection without enzyme sensor is: utilize electrochemical workstation, W1 is applied step voltage by the method adopting step voltage on W1, initial voltage is 0v, step voltage is 0.7 ~ 0.9v, and snap time is 10 ~ 30s; Meanwhile, when adopting on W2, W2 is applied constant voltage by m-current methods, and voltage is 0 ~ 0.6v; Adding hydrogenperoxide steam generator to be measured in electrolyzer, the electric current on W2 can increase accordingly along with the increase of concentration of hydrogen peroxide, and increasing according to gained electric current is worth hydrogenperoxide steam generator concentration to be measured.
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