CN104820006B - A kind of preparation method and application of the Optical Electro-Chemistry sensor of Sensitive Detection Cd2+ based on ZnO and CdS composite semiconductor material - Google Patents
A kind of preparation method and application of the Optical Electro-Chemistry sensor of Sensitive Detection Cd2+ based on ZnO and CdS composite semiconductor material Download PDFInfo
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Abstract
The invention belongs to functionalized nano material, sensing is analyzed and environmental analysis field, and it provides a kind of Sensitive Detection Cd based on ZnO and CdS composite semiconductor material2+The preparation method of Optical Electro-Chemistry sensor and detection.Described sensor production scheme is: with ITO electrode as substrate, be inoculated in ITO electrode by ZnO crystal seed, by using NaS2SO3As sulphur source, the Cd in environmental sample2+As cadmium source, CdS as stabilizer, is deposited to, in the ITO electrode of ZnO crystallization, make photosignal significantly be strengthened by EDTA by electro-deposition method, and detection range is 0.01 ~ 5.0mmol/L, and detection limit is up to 5 mol/L.
Description
Technical field
The invention belongs to functionalized nano material, sensing is analyzed and environmental analysis field, is specifically related to based on a kind of Sensitive Detection Cd2+The preparation of Optical Electro-Chemistry sensor and application.
Background technology
Cadmium is the heavy metal that toxicity is the strongest, is the nonessential toxic element of human body, is referred to as " first of the five poisonous creatures: scorpion, viper, centipede, house lizard, toad ", and by the world, the labour health heavy metal committee is set to priority pollutant.It is reported, can cause slow poisoning at the cadmium ion being enriched with in human body by biological chain, make kidney hypofunction, osteoporosis, the long-term caddy that sucks can cause lung inflammation, bronchitis even cancer, moreover it is possible to causes the diseases such as diabetes, hypertension.So a kind of method designing easy detection cadmium ion is critically important.
Optical Electro-Chemistry refers to that molecule, ion or semi-conducting material etc. make electronics be stimulated the charge transfer produced because absorbing photon, thus realizes the luminous energy conversion process to electric energy.Have after the active material light of Optical Electro-Chemistry excites and separation of charge or charge transfer process occur, thus form voltage or photoelectric current.
ZnO is a kind of novel direct semiconductor material with wide forbidden band, energy gap under room temperature is 3.3 eV, exciton bind energy is about 60 eV, it is expected to develop the multiple luminescent devices such as blue light, blue green light, ultraviolet light, it is expected to become follow-on photoelectric device, it is widely used in the fields such as photoelectric communication network, photoelectric display, photoelectricity storage, photoelectric conversion and photodetection, the most deeply by the extensive concern of people.
Cadmium sulfide is a kind of important semiconductor functional material, and high-purity cadmium sulfide has strong photoelectric effect, can be used for photoelectric tube processed, solar cell visible ray.
The present invention uses NaS2SO3As sulphur source, directly use the Cd in environmental sample2+As cadmium source, CdS is deposited to the surface of ZnO nanorod, form ZnO/CdS composite so that it is there is higher electricity conversion.Cd2+Concentration is different, and the amount of the CdS depositing to the surface of ZnO nanorod is different, and the photo-current intensity of Photoelectric Detection is the most different, thus realizes Cd2+Quantitative detection.
Summary of the invention
Technical scheme, comprises the following steps.
1. Sensitive Detection Cd based on ZnO and CdS composite semiconductor material2+The preparation method of Optical Electro-Chemistry sensor, comprise the following steps:
(1) pretreatment of ITO electrode: ito glass is slit into 3 cm × 0.8 cm sizes, successively with acetone, NaOH ethanol solution, deionized water ultrasonic cleaning 15 min, dries up with nitrogen；
(2) weighing the NaOH of 0.02 ~ 0.03 g, the zinc acetate of 0.04 ~ 0.05 g is dissolved in 10 mL methyl alcohol respectively, obtains NaOH methanol solution and zinc acetate methanol solution；Drop to NaOH methanol solution, in zinc acetate methanol solution, be heated to reflux 2 ~ 3 h at 55 ~ 65 DEG C, be cooled to room temperature, obtain ZnO crystal seed；
(3) pretreated ITO electrode is vertically put in ZnO crystal seed, soak 1 ~ 5 min, take out, dry under infrared lamp, repeat 3 ~ 6 times, make ZnO crystal seed on ito glass surface seeding；Then calcine 20 ~ 50 min, cooling at 300 ~ 400 DEG C, obtain the ITO electrode of ZnO crystallization；
(4) ITO electrode of ZnO crystallization is put in the reactor containing 5 mL zinc nitrates-hexamethylenetetramine mixed liquor, heat 5 ~ 7 h, cooling at 90 DEG C, with deionized water rinsing, natural drying, obtain white film, i.e. prepare one detection Cd2+Optical Electro-Chemistry sensor；
Described zinc nitrate-hexamethylenetetramine mixed liquor, is that the hexamethylenetetramine aqueous solution of the zinc nitrate aqueous solution by 0.10 mol/L and 0.10 mol/L is mixed to prepare according to the ratio of 1 ~ 5:1.
2. Cd2+Detecting step as follows:
(1) Cd2+The preparation of deposition solution: take the Cd of 0.01-5.0 mmol/L2+Standard liquid, adds the sulphur source Na of 5-10 mmol/L2S2O3With stabilizer EDTA, prepare Cd2+Deposition solution；
(2) using three electrodes, in three electrodes, saturated calomel electrode is reference electrode, and platinum electrode is auxiliary electrode, and ITO electrode is working electrode, at the Cd that (1) obtains2+In deposition solution, using i-t curve method to carry out electro-deposition, sedimentation potential is-1.06 V, and sedimentation time is 100 s；
(3) by post-depositional ITO electrode deionized water rinsing, and dry under infrared lamp；
(4) using i-t curve method to carry out Photoelectric Detection, bias is set to 0 V；The changing value of electric current before and after 10 s switch lamps, record switch lamp, according to the Cd of variable concentrations2+The different photocurrent values that deposition solution produces, drawing curve；
(5) Cd is replaced with testing sample2+Standard liquid, carries out sample detection according to the method for step (1) ~ (4).
The useful achievement of the present invention
(1) use the preparation of ZnO array modified electrode for Sensitive Detection Cd first2+Optical Electro-Chemistry sensor.
(2) the Optical Electro-Chemistry sensor of the detection cadmium ion that prepared by the present invention, it is possible to achieve simple, quick and high-sensitivity detection, the range of linearity is 0.01 mmol/L ~ 5 mmol/L, and detection is limited to 5 mol/L.
(3) sensor prepared by can realize for Cd in visible region2+Sensitive Detection, substantially increase the possibility of its actual application.
Specific embodiments
Embodiment 1A kind of Sensitive Detection Cd based on ZnO and CdS composite semiconductor material2+The preparation method of Optical Electro-Chemistry sensor
(1) ito glass is cut into 3 cm × 0.8 cm sizes, according to this with acetone, NaOH ethanol solution, deionized water ultrasonic cleaning 15 min, dries up with nitrogen, obtain the ITO electrode of pretreatment；
(2) weigh the NaOH of 0.02 g, the zinc acetate of 0.04 g is dissolved in 10 mL methyl alcohol respectively, obtains NaOH methanol solution and zinc acetate methanol solution；At 55 DEG C, NaOH methanol solution is dropped in zinc acetate methanol solution, return stirring 2 h, transfer them to, in beaker, be cooled to room temperature, obtain the opalescent colloidal containing ZnO crystal seed；
(3) pretreated ITO electrode is vertically put in the opalescent colloidal containing ZnO crystal seed, soak 1 min, take out, dry under infrared lamp, be repeated 4 times, make ZnO crystal seed on ito glass surface seeding；Put it into porcelain boat, be placed in Muffle furnace, 300 DEG C of calcining 20 min, cool down, take out, obtain the ITO electrode of ZnO crystallization；
(4) ITO electrode of ZnO crystallization is put in the reactor containing 5 mL zinc nitrates-hexamethylenetetramine solution, 90 DEG C of heating 5 h, cool down, take out, with deionized water rinsing, natural drying, obtains on ITO electrode surface solidifying white film, prepares one detection Cd2+Optical Electro-Chemistry sensor；
Described zinc nitrate-hexamethylenetetramine solution, is that the hexamethylenetetramine aqueous solution of the zinc nitrate aqueous solution by 0.10 mol/L and 0.10 mol/L is mixed to prepare according to the ratio of 1:1.
Embodiment 2A kind of Sensitive Detection Cd based on ZnO and CdS composite semiconductor material2+The preparation method of Optical Electro-Chemistry sensor
(1) ito glass is cut into 3 cm × 0.8 cm sizes, according to this with acetone, NaOH ethanol solution, deionized water ultrasonic cleaning 15 min, dries up with nitrogen, obtain the ITO electrode of pretreatment；
(2) weigh the NaOH of 0.03 g, the zinc acetate of 0.05 g is dissolved in 10 mL methyl alcohol respectively, obtains NaOH methanol solution and zinc acetate methanol solution；At 60 DEG C, NaOH methanol solution is dropped in zinc acetate methanol solution, return stirring 2.5 h, transfer them to, in beaker, be cooled to room temperature, obtain the opalescent colloidal containing ZnO crystal seed；
(3) pretreated ITO electrode is vertically put in the opalescent colloidal containing ZnO crystal seed, soak 3 min, take out, dry under infrared lamp, be repeated 5 times, make ZnO crystal seed on ito glass surface seeding；Put it into porcelain boat, be placed in Muffle furnace, 350 DEG C of calcining 35 min, cool down, take out, obtain the ITO electrode of ZnO crystallization；
(4) ITO electrode of ZnO crystallization is put in the reactor containing 5 mL zinc nitrates-hexamethylenetetramine solution, 90 DEG C of heating 6 h, cool down, take out, with deionized water rinsing, natural drying, obtains on ITO electrode surface solidifying white film, prepares one detection Cd2+Optical Electro-Chemistry sensor；
Described zinc nitrate-hexamethylenetetramine solution, is that the hexamethylenetetramine aqueous solution of the zinc nitrate aqueous solution by 0.10 mol/L and 0.10 mol/L is mixed to prepare according to the ratio of 3:1.
Embodiment 3A kind of Sensitive Detection Cd based on ZnO and CdS composite semiconductor material2+The preparation method of Optical Electro-Chemistry sensor
(1) ito glass is cut into 3 cm × 0.8 cm sizes, according to this with acetone, NaOH ethanol solution, deionized water ultrasonic cleaning 15 min, dries up with nitrogen, obtain the ITO electrode of pretreatment；
(2) weigh the NaOH of 0.030 g, the zinc acetate of 0.05 g is dissolved in 10 mL methyl alcohol respectively, obtains NaOH methanol solution and zinc acetate methanol solution；At 65 DEG C, NaOH methanol solution is dropped in zinc acetate methanol solution, return stirring 3 h, transfer them to, in beaker, be cooled to room temperature, obtain the opalescent colloidal containing ZnO crystal seed；
(3) pretreated ITO electrode is vertically put in the opalescent colloidal containing ZnO crystal seed, soak 5 min, take out, dry under infrared lamp, be repeated 6 times, make ZnO crystal seed on ito glass surface seeding；Put it into porcelain boat, be placed in Muffle furnace, 400 DEG C of calcining 50 min, cool down, take out, obtain the ITO electrode of ZnO crystallization；
(4) ITO electrode of ZnO crystallization is put in the reactor containing 5 mL zinc nitrates-hexamethylenetetramine solution, 90 DEG C of heating 7 h, cool down, take out, with deionized water rinsing, natural drying, obtains on ITO electrode surface solidifying white film, prepares one detection Cd2+Optical Electro-Chemistry sensor；
Described zinc nitrate-hexamethylenetetramine solution, is that the hexamethylenetetramine aqueous solution of the zinc nitrate aqueous solution by 0.10 mol/L and 0.10 mol/L is mixed to prepare according to the ratio of 5:1.
Embodiment 4 Cd2+The drafting of calibration curve
(1) Cd2+The preparation of deposition solution
Take the Cd of 0.01 ~ 5.0 mmol/L2+Standard liquid, adds the sulphur source Na of 10 mmol/L2S2O3With stabilizer EDTA, prepare Cd2+Deposition solution；
(2) using three electrodes, in three electrodes, saturated calomel electrode is reference electrode, and platinum electrode is auxiliary electrode, and ITO electrode is working electrode, at the Cd that (1) obtains2+In deposition solution, using i-t curve method to carry out electro-deposition, sedimentation potential is-1.06 V, and sedimentation time is 100 s；
(3) by post-depositional ITO electrode deionized water rinsing, and dry under infrared lamp；
(4) using i-t curve method to carry out Photoelectric Detection, bias is set to 0 V；The changing value of electric current before and after 10 s switch lamps, record switch lamp, according to the Cd of variable concentrations2+The different photocurrent values that deposition solution produces, drawing curve.
Embodiment 5 Cd2+The detecting step of content
Cd is replaced with testing sample2+Standard liquid, other is the same as in Example 4, acquired results comparison working curve, calculates Cd in sample2+Content.
Claims (2)
1. Sensitive Detection Cd based on ZnO and CdS composite semiconductor material2+The preparation method of Optical Electro-Chemistry sensor, it is characterised in that comprise the following steps:
(1) pretreatment of ITO electrode: ito glass is slit into 3 cm × 0.8 cm sizes, successively with acetone, NaOH ethanol solution, deionized water ultrasonic cleaning 15 min, dries up with nitrogen；
(2) weighing the NaOH of 0.02 ~ 0.03 g, the zinc acetate of 0.04 ~ 0.05 g is dissolved in 10 mL respectively
In methyl alcohol, obtain NaOH methanol solution and zinc acetate methanol solution；Drop to NaOH methanol solution, in zinc acetate methanol solution, be heated to reflux 2 ~ 3 h at 55 ~ 65 DEG C, be cooled to room temperature, obtain ZnO crystal seed；
(3) pretreated ITO electrode is vertically put in ZnO crystal seed, soak 1 ~ 5 min, take out, dry under infrared lamp, repeat 3 ~ 6 times, make ZnO crystal seed on ito glass surface seeding；Then calcine 20 ~ 50 min, cooling at 300 ~ 400 DEG C, obtain the ITO electrode of ZnO crystallization；
(4) ITO electrode of ZnO crystallization is put into containing 5 mL
In the reactor of zinc nitrate-hexamethylenetetramine mixed liquor, heat 5 ~ 7 h, cooling at 90 DEG C, with deionized water rinsing, natural drying, obtain white film；Described zinc nitrate-hexamethylenetetramine mixed liquor, is that the hexamethylenetetramine aqueous solution of the zinc nitrate aqueous solution by 0.10 mol/L and 0.10 mol/L is mixed to prepare according to the ratio of 1 ~ 5:1.
2. the Optical Electro-Chemistry sensor that prepared by preparation method as claimed in claim 1 is for Cd2+Detection, it is characterised in that step is as follows:
A () takes 0.01 ~ 5.0 mmol/L
Cd2+Standard liquid, adds 5 ~ 10 mmol/L
Sulphur source Na2S2O3With stabilizer EDTA, prepare Cd2+Deposition solution；
B () uses three electrodes, in three electrodes, saturated calomel electrode is reference electrode, and platinum electrode is auxiliary electrode, and ITO electrode is working electrode, the Cd obtained in above-mentioned steps (a)2+In deposition solution, using i-t curve method to carry out electro-deposition, sedimentation potential is-1.06V, and sedimentation time is 100 s；
C () is by post-depositional ITO electrode deionized water rinsing, and dry under infrared lamp；
D () uses i-t curve method to carry out Photoelectric Detection, bias is set to 0 V；The changing value of electric current before and after 10 s switch lamps, record switch lamp, according to the Cd of variable concentrations2+The different photocurrent values that deposition solution produces, drawing curve；
E () replaces Cd with testing sample2+Standard liquid, carries out sample detection according to the method for above-mentioned steps (a)-(d).
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| CN105806911B (en) * | 2016-05-09 | 2018-04-13 | 曲阜师范大学 | A kind of ZnO Au@CdS photoelectricity composite materials and its preparation method and application |
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| CN1500790A (en) * | 2002-11-15 | 2004-06-02 | 中国科学院化学研究所 | Zinc oxide nanometer rod, preparing method and application thereof |
| CN102412318A (en) * | 2011-12-15 | 2012-04-11 | 湖北大学 | ZnO/CdTe/CdS nanometer cable array electrode and preparation method thereof |
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| CN1500790A (en) * | 2002-11-15 | 2004-06-02 | 中国科学院化学研究所 | Zinc oxide nanometer rod, preparing method and application thereof |
| CN102412318A (en) * | 2011-12-15 | 2012-04-11 | 湖北大学 | ZnO/CdTe/CdS nanometer cable array electrode and preparation method thereof |
| CN103399062A (en) * | 2013-08-01 | 2013-11-20 | 台州学院 | Novel Pb2+ supersensitive detecting method based on photoelectrochemical sensing |
Non-Patent Citations (3)
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