CN106324050B - A kind of based single crystal TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods - Google Patents
A kind of based single crystal TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods Download PDFInfo
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Abstract
The present invention relates to a kind of based single crystal TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, specifically includes following steps：1) standard solution for preparing a series of test substance PCB101 of various concentrations, is sufficiently stirred, and stands；2) it is biased under ultraviolet light using current-time curvel method, measures (SC, MI) TiO2Photocurrent response of the NRs light anodes in the PCB101 standard solution of various concentration, and drawing curve；3) actual sample is prepared, is sufficiently stirred, is stood；4) it under ultraviolet light, is biased, measures (SC, MI) TiO2Photocurrent response of the NRs light anodes in actual sample, and according to the concentration of working curve calculating actual sample, then convert to obtain the concentration of test substance PCB101.Compared with prior art, the present invention goes out good selectivity, method is simple and practicable, high sensitivity, and detection limit reaches 10 by introducing molecular engram site in situ in monocrystalline photoanode surface to material exhibits to be measured‑ 14Mol/L, electrode are stablized, and have good reproducibility.
Description
Technical field
The invention belongs to nano material, photoelectrochemical assay and environmental monitoring technology fields, are related to a kind of based single crystal
TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, more particularly to it is a kind of based on molecular engram monocrystalline TiO2Nanometer rods light
The Polychlorinated biphenyls photoelectrochemical assay method of anode.
Background technology
Polychlorinated biphenyls (Polychlorinated biphenyls, PCBs) is the extremely stable chloro of a kind of chemical property
Compound fragrant hydrocarbon is one of the persistence organic pollutant of whole world extensive concern.PCBs has strong carcinogenic, teratogenesis
Toxicity, and lasting murder by poisoning can be finally generated to human body by the amplification of food chain, therefore, it is accurate in real time to be carried out to it
Detection, to environmental protection, find out in environment the pollution level of PCBs and to human body may caused by harm have it is extremely important
Meaning.PCBs has 209 kinds of homologues, and biochemical and toxicity reaction caused by each PCBs homologues is diversification and complicates
's.Since the 21th century, the choosing of single PCBs monomers has more been transferred to from the measurement of total amount for the focus of PCBs detections
Selecting property is analyzed.Currently, in addition to being widely accepted with high resolution spectral estimation joint technology (HRGC-HRMS)
Other than so-called " gold standard " of means, the highly sensitive highly selective Polychlorinated biphenyls that is convenient and efficient, being easy to miniaturization of exploitation
Sensing technology becomes research hotspot.
Photoelectric analysis is a kind of new analysis method to grow up on the basis of electrochemical method, due to the letter of its equipment
The advantages that on-line monitoring single, easy to operate, environmentally friendly and easy to implement, is of increased attention in analysis field.
Optical electro-chemistry combines traditional electro-catalysis and photocatalysis, not only has many advantages, such as electrochemical method, but also have again
The advantages of optical means, it is considered to be a kind of overdelicate analysis method is suitable for the extremely low analyte determination of concentration.Meanwhile
Since optical electro-chemistry has redox active more higher than single electro-catalysis or photocatalysis, live more suitable for non-electrochemical
The detection of property substance.Optical electro-chemistry is more advantageous to the sensitive current-responsive of acquisition for analyzing detection field, improves the spirit of detection
Sensitivity.
Although photo-electrocatalytic technology high catalytic efficiency, it has, and there are one notable disadvantages, i.e., in catalyst system and catalyzing
There is no selectivity for various substrates.And in analyte detection process, often substance to be detected and a variety of, even higher concentration
Chaff interferent coexists, and how using PhotoelectrochemicalMethod Method, to realize, certain low concentration high toxicity pollutant analyses are examined in pollution objects system
Survey is still a difficult point and emphasis for current photoelectric sense technology research.
Molecular engram (Molecular Imprinting) technology is the Molecular Recognization simulated present in nature, such as
Enzyme-to-substrate, antibody and antigen etc. have the molecular engram material of particular molecule identification function using target molecule as templated synthesis,
It is referred to as " artificial antibody ".Molecular imprinting technology because have unique identity and selectivity, bioengineering, clinical medicine,
It forms and is widely applied in natural drug separation, food industry and environmental monitoring.Currently, molecular imprinting technology is in selective electricity
It also wins initial success in catalysis and the research in photoelectrocatalysis field.Especially obtained in the selective absorption of Polychlorinated biphenyls with detaching
Preferable application.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of highly sensitive, high selections
Property, detection sensitivity are high based on molecular engram monocrystalline TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods light anode.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of based single crystal TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, this method is with Polychlorinated biphenyls 101
(PCB101) it is detection object, specifically includes following steps：
1) standard solution of the test substance PCB101 of various concentrations a series of is prepared, and is added separately to electrolytic cell successively
It is middle to be used as electrolyte, it is sufficiently stirred, stands；
2) it is biased under ultraviolet light using current versus time curve method, measures (SC, MI)-TiO2 NRs
Photocurrent response of the light anode in the PCB101 standard solution of various concentration, and according to the pass of photoelectric current and concentration of standard solution
It is drawing curve；
3) actual sample is prepared, and is added in electrolytic cell and is used as electrolyte, is sufficiently stirred, is stood；
4) it under ultraviolet light, is biased, measures (SC, MI)-TiO2Photoelectricity of the NRs light anodes in actual sample
Stream response, and according to working curve I/I0=0.862+0.059lgC (C is concentration, unit pM) calculates the dense of actual sample
Degree, wherein I are (SC, MI)-TiO2Photocurrent response of the NRs light anodes in actual sample, I0For (SC, MI)-TiO2NRs light
Photocurrent response of the anode in blank solution, then the concentration of test substance PCB101 is obtained by the concentration conversion of actual sample.
Described (SC, the MI)-TiO2The preparation method of NRs light anodes specifically includes following steps：
A one layer of TiO) is grown on FTO basal electrodes using sol-gel method2Crystal seed；
B it is) 1 by volume:1 deionized water and concentrated hydrochloric acid are mixed, then be added dropwise simultaneously butyl titanate and
PCB101 is stirred, and mixed solution is made；
C) first by step A) growth obtained has one layer of TiO2The FTO basal electrodes of crystal seed are placed in autoclave, then
Step B is added) made from mixed solution, sealing reacts 2-6h and under the conditions of 140-160 DEG C, waits for after reaction, taking out
Electrode cleans up, dry；
D) by step C) it is dry after electrode be placed in Muffle furnace, after calcining, be cooled to room temperature, obtain PCB101 points
(SC, MI)-TiO of sub- trace2NRs light anodes.
Step B) described in mixed solution in, the molar concentration of titanium ion is 35-70mM.
Step B) described in mixed solution in, the molar concentration of PCB101 is 1-5 μM.
Step B) described in concentrated hydrochloric acid mass fraction be 38wt%.
Step D) described in the treatment conditions of calcining be：Calcination temperature is 400-500 DEG C, calcination time 0.5-2h.
The bias is 0.6-0.8V.
The actual sample is the sample mixed liquor of test substance PCB101 and interfering substance.
In the sample mixed liquor, the concentration ratio of test substance PCB101 and interfering substance is 1:100.
The interfering substance includes PCB 126 (PCB126), Polychlorinated biphenyls 77 (PCB77), naphthalene, pyrene, 2,4- bis-
One in chlorophenoxyacetic acid (2,4-D), 2- chloro- 4- ethylamino-s -6- isopropylamine bases-s-triazine (Atrazine) or bisphenol-A
Kind.
The present invention is based on molecular engram monocrystalline TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods light anode, will contain
Have target molecule PCB101 or testing molecule to be measured and 100 times of concentration interfering substance (such as PCB126, PCB77, naphthalene, pyrene,
2,4-D, Atrazine and bisphenol-A etc.) mixed solution as electrolyte, be sufficiently stirred, so that testing molecule is in electrode table
The selective enrichment in face；It stands, opens ultraviolet source；The method (i.e. I-t curves) for selecting electric current-time graph, it is inclined applying
Under conditions of pressing (0.6V), photoelectric current is measured, to investigate the interference that other substances coexist for PCB101 photoelectric analysis.
The present invention passes through in single crystal titanium dioxide nanometer rods (i.e. TiO2NRs) surface in situ introduces PCB101 molecular engrams position
Point assigns the good selectivity of light anode, avoids that the interference of pollutant, especially PCBs homologues for detection coexists, and realizes
Highly sensitive, highly selective detection to PCB101, detection sensitivity reach 1 × 10-14Mol/L has good reproducibility.
Compared with prior art, the present invention has the following advantages that：
(1) by crystal seed induction and hydro-thermal method, in FTO substrates growth in situ molecular engram, it is upright orderly one-dimensional
Monocrystalline 1D-TiO2NRs, due to TiO2Surface can form the halogen key with orientation with the presence of a large amount of hydroxyl with PCB101,
Molecular engram site is formed, this molecular engram site not only has shape-selective selection index system, while utilizing template molecule and trace
The complementation of functional group between site can effectively reinforce supermolecular mechanism between the two, further increase selectivity.
(2) in the TiO of one-dimensional single crystal nanorod structure2Surface construction molecular engram site, mono-crystalline structures are conducive to molecule
The high quality of imprinted sites is expressed；One-dimentional structure is conducive to the separation of photo-generate electron-hole, improves photocurrent response, improves inspection
The sensitivity of survey；And directly in stable inorganic TiO2Surface introduces molecular engram, and electrode has good chemical stability.
(3) it is based on (SC, MI)-TiO2The Polychlorinated biphenyls photoelectric analysis method of NRs light anodes, passes through molecular engram site pair
The selective enrichment of testing molecule PCB101 acts on, and substantially increases selective enumeration method ability and the sensitivity of electrode so that
The electrode can selectively identify out testing molecule, wherein PCB101 in the interfering substance of 100 times of test substance concentration
Homologue PCB126 and PCB77 caused by the response of the optical electro-chemistry of testing molecule on influencing still less than 40%.
(4) present invention is by photoelectrochemical assay, realizes the detection of test substance PCB101, and the instrument of use is inexpensively just
It takes, method is simple and practicable, and has higher sensitivity, and detection limit reaches 10-14Mol/L, electrode are stablized, and with good
Reproducibility.
Description of the drawings
Fig. 1 is (SC, MI)-TiO produced by the present invention2The stereoscan photograph of NRs light anodes；
Fig. 2 is (SC, MI)-TiO produced by the present invention2NRs light anodes are being applied using interval and are not being applied ultraviolet lighting
In the case of photocurrent response variation diagram；
Fig. 3 is (SC, MI)-TiO produced by the present invention2Photoelectric current of the NRs light anodes in various concentration PCB101 solution
Response and photocurrent variations Δ I relational graphs；
Fig. 4 is (SC, MI)-TiO produced by the present invention2Δ I/ of the NRs light anodes in various concentration PCB101 solution
IblankWith the linear relationship chart of PCB101 log concentrations.
Specific implementation mode
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
A kind of based single crystal TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, working electrode (SC, MI)-
TiO2NRs light anodes are obtained by following steps：
One layer of TiO is grown by sol-gel process on FTO matrixes2Crystal seed.Then, by 7.5mL deionized waters and
7.5mL concentrated hydrochloric acids (38wt%) are mixed, then are added dropwise to 0.35mL butyl titanates.PCB101 is added simultaneously as template point
Son, a concentration of 3 μM.It is vigorously stirred 30min liquid clarifications to be mixed.Pretreated FTO is put into the polytetrafluoroethylene (PTFE) lining of 25mL
Among the autoclave at bottom, above-mentioned solution is poured into, reacts 4h under the conditions of 150 DEG C after sealing.Obtained electrode is distilled
Water cleans for several times, 60 DEG C of dryings, then the high-temperature calcination 0.5h at 500 DEG C in Muffle furnace, obtains (SC, MI)-TiO2NRs light sun
Pole, as shown in Figure 1, (SC, MI)-TiO2NRs light anodes are cubic nano bar-shape structure, grow comparatively dense uniform, diameter
About 60nm.
Embodiment 2
Using METHOD FOR CONTINUOUS DETERMINATION containing 1 × 10-10The 0.1mol/L Na of mol/L PCB1012SO4The side of photoelectric current in solution
Method, to (SC, MI)-TiO2The stability of NRs light anodes is studied.Under illumination condition, (SC, MI)-TiO2NRs light sun
Pole can show rapidly photocurrent response, under the illumination of continuous 50s, keep stable photoelectric current.Meanwhile using interval
The means for applying and not applying light source are found during continuously investigating photocurrent response situation, in continuous 15 scanning,
What photocurrent response value change substantially without, as shown in Fig. 2.Should the result shows that, the PCB101 optical electro-chemistry sensors constructed
With high stability.
Embodiment 3
A kind of based single crystal TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, using I-t curve methods, 0.6V
Under current potential and ultra violet lamp, in 0.1M Na2SO4In solution, the photoelectric current of background solution is measured, then uses micro-sampling successively
Device, toward Na2SO4A series of a concentration of 1 × 10 are added in solution-4Mol/L~1 × 10-10The PCB101 standard solution of mol/L,
Its photoelectric current is surveyed respectively.During the experiment, the increase with PCB101 concentration, (SC, MI)-TiO are found2NRs light anodes are examined
The photocurrent response measured gradually increases, as shown in Figure 3.
In Fig. 4, the linear fit equation Δ I/I of PCB101 detectionsblank=0.862+0.059logC, coefficient R2=
0.99787, detection range is 1.0 × 10-14~1.0 × 10-7Mol/L, detection are limited to 1.0 × 10-14mol/L。
Embodiment 4
By (SC, MI)-TiO of preparation2NRs light anodes are for detecting PCB101 and other pollutants.
Experimental implementation is：Every time to 10mL 0.1mol/L Na2SO4After being separately added into PCB101 in solution, concentration is added
It is PCB126, PCB77, naphthalene, pyrene, 2,4-D, Atrazine, the bisphenol-A of 100 times of PCB101 concentration, each interfering substance and PCB101
Two Component Systems are formed, are stirred, (SC, MI)-TiO is measured after turning on light2The photoelectric current (100s) of NRs light anodes, turns off the light simultaneously later
It is operated before repeating.
The above method can selectively identify out to be measured in 100 times of concentration in the interfering substance of test substance concentration
Molecule, and influence to be respectively less than 40% caused by responding the optical electro-chemistry of testing molecule.
Embodiment 5
A kind of based single crystal TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, this method is with Polychlorinated biphenyls 101
(PCB101) it is detection object, specifically includes following steps：
1) standard solution of the test substance PCB101 of various concentrations a series of is prepared, and is added separately to electrolytic cell successively
It is middle to be used as electrolyte, it is sufficiently stirred, stands；
2) current versus time curve method is used, under ultraviolet light, 0.6V is biased, measures (SC, MI)-
TiO2Photocurrent response of the NRs light anodes in the PCB101 standard solution of various concentration, and according to photoelectric current and standard solution
The relationship drawing curve of concentration；
3) actual sample is prepared, and is added in electrolytic cell and is used as electrolyte, is sufficiently stirred, is stood；
4) under ultraviolet light, it is biased 0.6V, measures (SC, MI)-TiO2NRs light anodes are in actual sample
Photocurrent response, and according to working curve I/I0=0.862+0.059lgC (units：C, pM) calculate actual sample concentration,
Middle I is (SC, MI)-TiO2Photocurrent response of the NRs light anodes in actual sample, I0For (SC, MI)-TiO2NRs light anodes
Photocurrent response in blank solution, then the concentration of test substance PCB101 is obtained by the concentration conversion of actual sample.
Described (SC, the MI)-TiO2The preparation method of NRs light anodes specifically includes following steps：
A one layer of TiO) is grown on FTO basal electrodes using sol-gel method2Crystal seed；
B it is) 1 by volume:1 deionized water and concentrated hydrochloric acid are mixed, then be added dropwise simultaneously butyl titanate and
PCB101 is stirred, and mixed solution is made；
C) first by step A) growth obtained has one layer of TiO2The FTO basal electrodes of crystal seed are placed in autoclave, then
Step B is added) made from mixed solution, sealing reacts 4h and under the conditions of 150 DEG C, waits for after reaction, taking out electrode, clearly
Wash clean, it is dry；
D) by step C) it is dry after electrode be placed in Muffle furnace, after calcining, be cooled to room temperature, obtain PCB101 points
(SC, MI)-TiO of sub- trace2NRs light anodes.
Step B) in, the molar concentration of titanium ion is 70mM in mixed solution, and the molar concentration of PCB101 is 5 μM；Dense salt
The mass fraction of acid is 38wt%.
Step D) in, the treatment conditions of calcining are：Calcination temperature is 500 DEG C, calcination time 0.5h.
Actual sample is the sample mixed liquor of test substance PCB101 and interfering substance, in the sample mixed liquor, determinand
The concentration ratio of matter PCB101 and interfering substance is 1:100.
In the present embodiment, interfering substance PCB126.
Embodiment 6
A kind of based single crystal TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, this method is with Polychlorinated biphenyls 101
(PCB101) it is detection object, specifically includes following steps：
1) standard solution of the test substance PCB101 of various concentrations a series of is prepared, and is added separately to electrolytic cell successively
It is middle to be used as electrolyte, it is sufficiently stirred, stands；
2) current versus time curve method is used, under ultraviolet light, 0.8V is biased, measures (SC, MI)-
TiO2Photocurrent response of the NRs light anodes in the PCB101 standard solution of various concentration, and according to photoelectric current and standard solution
The relationship drawing curve of concentration；
3) actual sample is prepared, and is added in electrolytic cell and is used as electrolyte, is sufficiently stirred, is stood；
4) under ultraviolet light, it is biased 0.8V, measures (SC, MI)-TiO2NRs light anodes are in actual sample
Photocurrent response, and according to working curve I/I0=0.862+0.059lgC (units：C, pM) calculate actual sample concentration,
In, I is (SC, MI)-TiO2Photocurrent response of the NRs light anodes in actual sample, I0For (SC, MI)-TiO2NRs light anodes
Photocurrent response in blank solution, then the concentration of test substance PCB101 is obtained by the concentration conversion of actual sample.
Described (SC, the MI)-TiO2The preparation method of NRs light anodes specifically includes following steps：
A one layer of TiO) is grown on FTO basal electrodes using sol-gel method2Crystal seed；
B it is) 1 by volume:1 deionized water and concentrated hydrochloric acid are mixed, then be added dropwise simultaneously butyl titanate and
PCB101 is stirred, and mixed solution is made；
C) first by step A) growth obtained has one layer of TiO2The FTO basal electrodes of crystal seed are placed in autoclave, then
Step B is added) made from mixed solution, sealing reacts 6h and under the conditions of 140 DEG C, waits for after reaction, taking out electrode, clearly
Wash clean, it is dry；
D) by step C) it is dry after electrode be placed in Muffle furnace, after calcining, be cooled to room temperature, obtain PCB101 points
(SC, MI)-TiO of sub- trace2NRs light anodes.
Step B) in, the molar concentration of titanium ion is 35mM in mixed solution, and the molar concentration of PCB101 is 1 μM；Dense salt
The mass fraction of acid is 38wt%.
Step D) in, the treatment conditions of calcining are：Calcination temperature is 400 DEG C, calcination time 2h.
Actual sample is the sample mixed liquor of test substance PCB101 and interfering substance, in the sample mixed liquor, determinand
The concentration ratio of matter PCB101 and interfering substance is 1:100.
In the present embodiment, interfering substance PCB77.
Embodiment 7
A kind of based single crystal TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, this method is with Polychlorinated biphenyls 101
(PCB101) it is detection object, specifically includes following steps：
1) standard solution of the test substance PCB101 of various concentrations a series of is prepared, and is added separately to electrolytic cell successively
It is middle to be used as electrolyte, it is sufficiently stirred, stands；
2) current versus time curve method is used, under ultraviolet light, 0.7V is biased, measures (SC, MI)-
TiO2Photocurrent response of the NRs light anodes in the PCB101 standard solution of various concentration, and according to photoelectric current and standard solution
The relationship drawing curve of concentration；
3) actual sample is prepared, and is added in electrolytic cell and is used as electrolyte, is sufficiently stirred, is stood；
4) under ultraviolet light, it is biased 0.7V, measures (SC, MI)-TiO2NRs light anodes are in actual sample
Photocurrent response, and according to working curve I/I0=0.862+0.059lgC (units：C, pM) calculate actual sample concentration,
In, I is (SC, MI)-TiO2Photocurrent response of the NRs light anodes in actual sample, I0For (SC, MI)-TiO2NRs light anodes
Photocurrent response in blank solution, then the concentration of test substance PCB101 is obtained by the concentration conversion of actual sample.
Described (SC, the MI)-TiO2The preparation method of NRs light anodes specifically includes following steps：
A one layer of TiO) is grown on FTO basal electrodes using sol-gel method2Crystal seed；
B it is) 1 by volume:1 deionized water and concentrated hydrochloric acid are mixed, then be added dropwise simultaneously butyl titanate and
PCB101 is stirred, and mixed solution is made；
C) first by step A) growth obtained has one layer of TiO2The FTO basal electrodes of crystal seed are placed in autoclave, then
Step B is added) made from mixed solution, sealing reacts 5h and under the conditions of 148 DEG C, waits for after reaction, taking out electrode, clearly
Wash clean, it is dry；
D) by step C) it is dry after electrode be placed in Muffle furnace, after calcining, be cooled to room temperature, obtain PCB101 points
(SC, MI)-TiO of sub- trace2NRs light anodes.
Step B) in, the molar concentration of titanium ion is 40mM in mixed solution, and the molar concentration of PCB101 is 2 μM, dense salt
The mass fraction of acid is 38wt%.
Step D) in, the treatment conditions of calcining are：Calcination temperature is 460 DEG C, calcination time 1.5h.
Actual sample is the sample mixed liquor of test substance PCB101 and interfering substance, in the sample mixed liquor, determinand
The concentration ratio of matter PCB101 and interfering substance is 1:100.
In the present embodiment, interfering substance 2,4-D.
Embodiment 8
A kind of based single crystal TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, this method is with Polychlorinated biphenyls 101
(PCB101) it is detection object, specifically includes following steps：
1) standard solution of the test substance PCB101 of various concentrations a series of is prepared, and is added separately to electrolytic cell successively
It is middle to be used as electrolyte, it is sufficiently stirred, stands；
2) current versus time curve method is used, under ultraviolet light, 0.6V is biased, measures (SC, MI)-
TiO2Photocurrent response of the NRs light anodes in the PCB101 standard solution of various concentration, and according to photoelectric current and standard solution
The relationship drawing curve of concentration；
3) actual sample is prepared, and is added in electrolytic cell and is used as electrolyte, is sufficiently stirred, is stood；
4) under ultraviolet light, it is biased 0.6V, measures (SC, MI)-TiO2NRs light anodes are in actual sample
Photocurrent response, and according to working curve I/I0=0.862+0.059lgC (units：C, pM) calculate actual sample concentration,
In, I is (SC, MI)-TiO2Photocurrent response of the NRs light anodes in actual sample, I0For (SC, MI)-TiO2NRs light anodes
Photocurrent response in blank solution, then the concentration of test substance PCB101 is obtained by the concentration conversion of actual sample.
Described (SC, the MI)-TiO2The preparation method of NRs light anodes specifically includes following steps：
A one layer of TiO) is grown on FTO basal electrodes using sol-gel method2Crystal seed；
B it is) 1 by volume:1 deionized water and concentrated hydrochloric acid are mixed, then be added dropwise simultaneously butyl titanate and
PCB101 is stirred, and mixed solution is made；
C) first by step A) growth obtained has one layer of TiO2The FTO basal electrodes of crystal seed are placed in autoclave, then
Step B is added) made from mixed solution, sealing reacts 3h and under the conditions of 152 DEG C, waits for after reaction, taking out electrode, clearly
Wash clean, it is dry；
D) by step C) it is dry after electrode be placed in Muffle furnace, after calcining, be cooled to room temperature, obtain PCB101 points
(SC, MI)-TiO of sub- trace2NRs light anodes.
Step B) in, the molar concentration of titanium ion is 45mM in mixed solution, and the molar concentration of PCB101 is 3 μM, dense salt
The mass fraction of acid is 38wt%.
Step D) in, the treatment conditions of calcining are：Calcination temperature is 480 DEG C, calcination time 1h.
Actual sample is the sample mixed liquor of test substance PCB101 and interfering substance, in the sample mixed liquor, determinand
The concentration ratio of matter PCB101 and interfering substance is 1:100.
In the present embodiment, interfering substance is Atrazine.
Claims (9)
1. a kind of based single crystal TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, which is characterized in that this method with
PCB101 is detection object, specifically includes following steps：
1) standard solution of the test substance PCB101 of various concentrations a series of is prepared, and is added separately to make in electrolytic cell successively
It for electrolyte, is sufficiently stirred, stands；
2) it is biased under ultraviolet light using current versus time curve method, measures (SC, MI)-TiO2NRs light anodes
Photocurrent response in the PCB101 standard solution of various concentration, and drawn according to the relationship of photoelectric current and concentration of standard solution
Working curve；
3) actual sample is prepared, and is added in electrolytic cell and is used as electrolyte, is sufficiently stirred, is stood；
4) it under ultraviolet light, is biased, measures (SC, MI)-TiO2Photoelectric current of the NRs light anodes in actual sample is rung
It answers, and according to working curve I/I0=0.862+0.059lgC calculates the concentration of actual sample, wherein I is (SC, MI)-
TiO2Photocurrent response of the NRs light anodes in actual sample, I0For (SC, MI)-TiO2NRs light anodes are in blank solution
Photocurrent response, then the concentration of test substance PCB101 is obtained by the concentration conversion of actual sample；
Wherein, SC is monocrystalline, and MI is molecular engram.
2. a kind of based single crystal TiO according to claim 12The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, it is special
Sign is, described (SC, the MI)-TiO2The preparation method of NRs light anodes specifically includes following steps：
A one layer of TiO) is grown on FTO basal electrodes using sol-gel method2Crystal seed；
B it is) 1 by volume:1 deionized water and concentrated hydrochloric acid are mixed, then butyl titanate and PCB101 is added dropwise simultaneously, fill
Divide and stir evenly, mixed solution is made；
C) first by step A) growth obtained has one layer of TiO2The FTO basal electrodes of crystal seed are placed in autoclave, add step
Rapid B) made from mixed solution, sealing reacts 2-6h and under the conditions of 140-160 DEG C, waits for after reaction, taking out electrode, clearly
Wash clean, it is dry；
D) by step C) it is dry after electrode be placed in Muffle furnace, after calcining, be cooled to room temperature, obtain PCB101 molecular engrams
(SC, MI)-TiO2NRs light anodes.
3. a kind of based single crystal TiO according to claim 22The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, it is special
Sign is, step B) described in mixed solution in, the molar concentration of titanium ion is 35-70mM.
4. a kind of based single crystal TiO according to claim 22The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, it is special
Sign is, step B) described in mixed solution in, the molar concentration of PCB101 is 1-5 μM.
5. a kind of based single crystal TiO according to claim 22The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, it is special
Sign is, step D) described in the treatment conditions of calcining be：Calcination temperature is 400-500 DEG C, calcination time 0.5-2h.
6. a kind of based single crystal TiO according to claim 12The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, it is special
Sign is that the bias is 0.6-0.8V.
7. a kind of based single crystal TiO according to claim 12The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, it is special
Sign is that the actual sample is the sample mixed liquor of test substance PCB101 and interfering substance.
8. a kind of based single crystal TiO according to claim 72The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, it is special
Sign is, in the sample mixed liquor, the concentration ratio of test substance PCB101 and interfering substance is 1:100.
9. a kind of based single crystal TiO according to claim 7 or 82The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods,
It is characterized in that, the interfering substance includes one in PCB126, PCB77, naphthalene, pyrene, 2,4-D, Atrazine or bisphenol-A
Kind.
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| CN110865103B (en) * | 2019-11-19 | 2021-02-02 | 山西大学 | Photoelectrochemical analysis method for selectively detecting pesticide atrazine |
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