CN106324050A - Monocrystalline TiO2 nanometer rod-based polychlorinated biphenyl photoelectrochemistry analysis method - Google Patents
Monocrystalline TiO2 nanometer rod-based polychlorinated biphenyl photoelectrochemistry analysis method Download PDFInfo
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Abstract
The invention relates to a monocrystalline TiO2 nanometer rod-based polychlorinated biphenyl photoelectrochemistry analysis method. The method comprises 1, preparing a series of tested PCB101 standard solutions with different concentrations, fully stirring the solutions and standing the mixture, 2, determining photocurrent response of a (SC, MI)-TiO2NRs photo anode in the tested PCB101 standard solutions with different concentrations under ultraviolet irradiation and bias voltage through a current-time curve method and drawing a work curve, 3, preparing a practical sample, fully stirring the sample and standing the sample, and 4, determining photocurrent response of the (SC, MI)-TiO2NRs photo anode under ultraviolet irradiation and bias voltage, calculating a practical sample concentration according to the work curve and carrying out conversion to obtain a concentration of a substance PCB101 to be detected. Compared with the prior art, the method introduces a molecular imprinting locus to the surface of the monocrystalline photo anode in situ, has good selectivity to the substance to be detected, has simple and easy processes, high sensitivity, a detection limit of 10<-14>mol/L, utilizes a stable electrode and has good reappearance.
Description
Technical field
The invention belongs to nano material, photoelectrochemical assay and environmental monitoring technology field, relate to a kind of based on list
Brilliant TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, particularly relates to a kind of based on molecular engram monocrystalline
TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods light anode.
Background technology
Polychlorinated biphenyls (Polychlorinated biphenyls, PCBs) is the chloro that a class chemical property is extremely stable
Compound fragrant hydrocarbon, is one of the persistence organic pollutant of whole world extensive concern.PCBs has strong
Carcinogenic, Teratogenesis toxicity, it is possible to by the murder by poisoning that the amplification of food chain is finally lasting to human body generation, therefore,
Carry out detecting accurately in real time to it, the pollution level of to environmental conservation, findding out PCBs in environment and can to human body
The harm that can cause has very important significance.PCBs has 209 kinds of homologues, each PCBs homologue
The biochemistry caused and toxicity reaction are variations and complicate.Since entering 21 century, PCBs is detected
Focus more transferred to the selectivity analysis of single PCBs monomer from the mensuration of total amount.At present, except by extensively
General acceptance with the high resolution spectral estimation multiple techniques (HRGC-HRMS) what is called as means
Beyond " golden standard ", develop the Polychlorinated biphenyls sensing that highly sensitive height is the most convenient and swift, be prone to miniaturization
Technology becomes study hotspot.
Photoelectric analysis is a kind of new analysis method grown up on the basis of electrochemical method, due to its equipment
Be simple and convenient to operate, environmentally friendly and easily realize the advantages such as on-line monitoring and receive increasingly at analysis field
Many concerns.Traditional electro-catalysis and photocatalysis are combined by Optical Electro-Chemistry, not only have all of electrochemical method
Many advantages, and have again the advantage of optical means it is considered to be a kind of overdelicate analysis method, it is suitable for concentration
Extremely low analyte determination.Simultaneously as Optical Electro-Chemistry has oxidation more higher than single electro-catalysis or photocatalysis
Reducing activity, it is more suitable for the detection of non-electroactive material.Optical Electro-Chemistry is used for analyzing detection field more to be had
It is beneficial to obtain sensitive current-responsive, improves the sensitivity of detection.
Although, photo-electrocatalytic technology catalytic efficiency is high, but it has a significant shortcoming, i.e. to catalyst system and catalyzing
In various substrates there is not selectivity.And in analyte detection process, material the most to be detected is with multiple, very
Chaff interference to higher concentration coexists, and how to utilize PhotoelectrochemicalMethod Method to realize some low concentration in pollutant system
High toxicity pollutant analysis detection remains a difficult point and the emphasis of current photoelectric sense technology research.
Molecular engram (Molecular Imprinting) technology is simulation Molecular Recognization existing for nature,
Such as enzyme-to-substrate, antibody and antigen etc., there is with target molecule for templated synthesis the molecule of particular molecule identification function
Imprinted material, is referred to as " artificial antibody ".Molecular imprinting because of have uniqueness identity and selectivity,
The separation of biological engineering, clinical medicine, natural drug, food industry and environmental monitoring define and is widely applied.
At present, molecular imprinting also wins initial success in the research in selectivity electro-catalysis and photoelectrocatalysis field.Especially
Selective absorption at Polychlorinated biphenyls has obtained preferable application with separating.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and a kind of highly sensitive, Gao Xuan is provided
Selecting property, detection sensitivity high based on molecular engram monocrystalline TiO2The Polychlorinated biphenyls Optical Electro-Chemistry of nanometer rods light anode
Analysis method.
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, the method is with Polychlorinated biphenyls
101 (PCB101) are detection object, specifically include following steps:
1) prepare the standard solution of the test substance PCB101 of a series of variable concentrations, and be added separately to successively
As electrolyte in electrolyzer, it is sufficiently stirred for, stands；
2) use current versus time curve method, under ultraviolet light irradiates, be biased, measure (SC, MI)-TiO2
NRs light anode photocurrent response in the PCB101 standard solution of variable concentrations, and according to photoelectric current and standard
The relation drawing curve of solution concentration；
3) preparation actual sample, and join as electrolyte in electrolyzer, it is sufficiently stirred for, stands；
4) under ultraviolet light irradiates, it is biased, measures (SC, MI)-TiO2NRs light anode is in actual sample
Photocurrent response, and according to working curve I/I0=0.862+0.059lgC (C is concentration, and unit is pM) calculates
The concentration of actual sample, wherein I is (SC, MI)-TiO2NRs light anode photocurrent response in actual sample,
I0For (SC, MI)-TiO2NRs light anode photocurrent response in blank solution, then changed by the concentration of actual sample
Calculate the concentration obtaining test substance PCB101.
Described (SC, MI)-TiO2The preparation method of NRs light anode specifically includes following steps:
A) sol-gel process is used to grow one layer of TiO on FTO basal electrode2Crystal seed；
B) be 1:1 by volume by deionized water and concentrated hydrochloric acid mix and blend, then be simultaneously added dropwise butyl titanate and
PCB101, stirs, and prepares mixed solution；
C) first by step A) prepared growth has one layer of TiO2The FTO basal electrode of crystal seed is placed in reaction under high pressure
In still, add step B) prepared mixed solution, seal, and under the conditions of 140-160 DEG C, react 2-6h,
After question response terminates, take out electrode, clean up, be dried；
D) by step C) dried electrode is placed in Muffle furnace, after calcining, is cooled to room temperature, i.e. prepares PCB101
(SC, MI)-TiO of molecular engram2NRs light anode.
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 the mass fraction of concentrated hydrochloric acid be 38wt%.
Step D) described in the treatment conditions of calcining be: calcining heat is 400-500 DEG C, and calcination time is 0.5-2h.
Described bias is 0.6-0.8V.
Described actual sample is the sample mix liquid of test substance PCB101 and interfering material.
In described sample mix liquid, the concentration of test substance PCB101 and interfering material is than for 1:100.
Described interfering material include PCB126 (PCB126), Polychlorinated biphenyls 77 (PCB77), naphthalene,
Pyrene, 2,4-dichlorphenoxyacetic acid (2,4-D), 2-chloro-4-ethylamino--6-isopropylamine base-s-triazine (G-30027)
Or the one in bisphenol-A.
The present invention is based on molecular engram monocrystalline TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods light anode,
By containing target molecule PCB101 to be measured or testing molecule and 100 times of concentration interfering material (as PCB126,
PCB77, naphthalene, pyrene, 2,4-D, G-30027 and bisphenol-A etc.) mixed solution as electrolyte, fully stir
Mix, be beneficial to the testing molecule selective enrichment at electrode surface；Stand, open ultraviolet source；Selection electric current-
The method (i.e. I-t curve) of time graph, under conditions of being biased (0.6V), measures photoelectric current, in order to
Investigate other materials interference for PCB101 photoanalysis that coexists.
The present invention is by single crystal titanium dioxide nanometer rods (i.e. TiO2NRs) surface in situ introducing PCB101 divides
Sub-imprinted sites, gives the selectivity that light anode is good, it is to avoid coexist pollutant, especially PCBs homologue pair
Interference in detection, it is achieved that the selective enumeration method highly sensitive, high to PCB101, detection sensitivity reaches 1 ×
10-14Mol/L, has good repeatability.
Compared with prior art, the present invention has the advantage that
(1) induced by crystal seed and hydro-thermal method, in FTO substrate growth in situ molecular engram, the most orderly
One-dimensional single crystal 1D-TiO2NRs, due to TiO2Surface, with the presence of substantial amounts of hydroxyl, can be formed with PCB101
Having the halogen key of orientation, form molecular engram site, this molecular engram site not only has shape-selective selection,
Utilize the complementation of functional group between template molecule and imprinted sites simultaneously, can effectively strengthen supermolecule between the two
Effect, improves selectivity further.
(2) at the TiO of one-dimensional single crystal nanorod structure2Surface construction molecular engram site, mono-crystalline structures is conducive to
The high-quality in molecular engram site is expressed；One-dimentional structure is conducive to the separation of photo-generate electron-hole, improves photoelectric current
Response, improves the sensitivity of detection；And directly at stable inorganic TiO2Surface introduces molecular engram, electrode
There is good chemical stability.
(3) based on (SC, MI)-TiO2The Polychlorinated biphenyls photoanalysis method of NRs light anode, passes through molecular engram
The site selective enrichment effect to testing molecule PCB101, substantially increase the selective enumeration method ability of electrode with
And sensitivity so that this electrode optionally can identify in the interfering material of 100 times of test substance concentration
Going out testing molecule, wherein the Optical Electro-Chemistry of testing molecule is responded by PCB101 homologue PCB126 and PCB77
The impact caused is still less than 40%.
(4) present invention passes through photoelectrochemical assay, it is achieved that the detection of test substance PCB101, the instrument of employing
Device is the most portable, and method is simple, and has higher sensitivity, and detection limit reaches 10-14Mol/L, electrode
Stable, and there is good repeatability.
Accompanying drawing explanation
Fig. 1 is (SC, MI)-TiO that the present invention prepares2The stereoscan photograph of NRs light anode；
Fig. 2 is (SC, MI)-TiO that the present invention prepares2NRs light anode is using interval to apply and is not applying ultraviolet
Photocurrent response variation diagram in the case of illumination；
Fig. 3 is (SC, MI)-TiO that the present invention prepares2NRs light anode is in variable concentrations PCB101 solution
Photocurrent response and photocurrent variations Δ I graph of a relation；
Fig. 4 is (SC, MI)-TiO that the present invention prepares2NRs light anode is in variable concentrations PCB101 solution
ΔI/IblankLinear relationship chart with PCB101 log concentration.
Detailed description of the invention
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, its working electrode (SC,
MI)-TiO2NRs light anode is obtained by following steps:
FTO matrix grows one layer of TiO by sol-gel process2Crystal seed.Then, 7.5mL is gone from
Sub-water and 7.5mL concentrated hydrochloric acid (38wt%) mix and blend, then it is added dropwise to 0.35mL butyl titanate.Simultaneously
PCB101 is as template molecule in addition, and concentration is 3 μMs.It is stirred vigorously the clarification of 30min liquid to be mixed.Will be pre-
Among the autoclave of the polytetrafluoroethylsubstrate substrate that the FTO processed puts into 25mL, pour above-mentioned solution into,
Under the conditions of 150 DEG C, 4h is reacted after sealing.Being cleaned for several times by the electrode distilled water obtained, 60 DEG C are dried,
High-temperature calcination 0.5h at 500 DEG C in Muffle furnace, obtains (SC, MI)-TiO again2NRs light anode, such as Fig. 1 institute
Show, (SC, MI)-TiO2NRs light anode is four directions nano bar-shape structure, grows comparatively dense homogeneous, its diameter
It is about 60nm.
Embodiment 2
Use METHOD FOR CONTINUOUS DETERMINATION containing 1 × 10-10The 0.1mol/L Na of mol/L PCB1012SO4Photoelectricity in solution
The method of stream, to (SC, MI)-TiO2The stability of NRs light anode is studied.Under illumination condition, (SC,
MI)-TiO2NRs light anode can show rapidly photocurrent response, under the illumination of continuous 50s, keeps stable
Photoelectric current.Meanwhile, in the means using interval to apply and do not apply light source, investigate photocurrent response situation continuously
During find, in the scanning of continuous 15 times, photocurrent response value does not has anything to change, such as Fig. 2 substantially
Shown in.This result shows, the PCB101 Optical Electro-Chemistry sensor constructed has high stability.
Embodiment 3
A kind of based single crystal TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, uses I-t curve method, 0.6V
Under current potential and ultra violet lamp, at 0.1M Na2SO4In solution, measure the photoelectric current of background solution, the most successively
With microsyringe, toward Na2SO4Adding a series of concentration in solution is 1 × 10-4Mol/L～1 × 10-10Mol/L's
PCB101 standard solution, surveys its photoelectric current respectively.In experimentation, find along with the increasing of PCB101 concentration
Add, (SC, MI)-TiO2The photocurrent response that NRs light anode detects is gradually increased, as shown in Figure 3.
In Fig. 4, the linear fit equation Δ I/I of PCB101 detectionblank=0.862+0.059logC, correlation coefficient
R2=0.99787, detection range is 1.0 × 10-14～1.0 × 10-7Mol/L, detection is limited to 1.0 × 10-14mol/L。
Embodiment 4
(SC, MI)-TiO by preparation2NRs light anode is for detecting PCB101 and other pollutant.
Experimental implementation is: every time to 10mL 0.1mol/L Na2SO4After solution is separately added into PCB101, then
Add concentration be the PCB126 of PCB101 concentration 100 times, PCB77, naphthalene, pyrene, 2,4-D, G-30027,
Bisphenol-A, each interfering material and PCB101 form two Component Systems, stir, and measure (SC, MI)-TiO after turning on light2
The photoelectric current (100s) of NRs light anode, turns off the light afterwards and repeats to operate before.
Said method can optionally identify and treat 100 times of concentration in the interfering material of test substance concentration
Survey molecule, and the Optical Electro-Chemistry of testing molecule is responded the impact caused be respectively less than 40%.
Embodiment 5
A kind of based single crystal TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, the method is with Polychlorinated biphenyls
101 (PCB101) are detection object, specifically include following steps:
1) prepare the standard solution of the test substance PCB101 of a series of variable concentrations, and be added separately to successively
As electrolyte in electrolyzer, it is sufficiently stirred for, stands；
2) use current versus time curve method, under ultraviolet light irradiates, be biased 0.6V, measure (SC,
MI)-TiO2NRs light anode photocurrent response in the PCB101 standard solution of variable concentrations, and according to photoelectricity
Stream and the relation drawing curve of concentration of standard solution；
3) preparation actual sample, and join as electrolyte in electrolyzer, it is sufficiently stirred for, stands；
4) under ultraviolet light irradiates, it is biased 0.6V, measures (SC, MI)-TiO2NRs light anode is at actual sample
Photocurrent response in product, and according to working curve I/I0=0.862+0.059lgC (unit: C, pM) calculates reality
The concentration of sample, wherein I is (SC, MI)-TiO2NRs light anode photocurrent response in actual sample, I0For
(SC,MI)-TiO2NRs light anode photocurrent response in blank solution, then by the concentration conversion of actual sample
Obtain the concentration of test substance PCB101.
Described (SC, MI)-TiO2The preparation method of NRs light anode specifically includes following steps:
A) sol-gel process is used to grow one layer of TiO on FTO basal electrode2Crystal seed；
B) be 1:1 by volume by deionized water and concentrated hydrochloric acid mix and blend, then be simultaneously added dropwise butyl titanate and
PCB101, stirs, and prepares mixed solution；
C) first by step A) prepared growth has one layer of TiO2The FTO basal electrode of crystal seed is placed in reaction under high pressure
In still, add step B) prepared mixed solution, seal, and under the conditions of 150 DEG C, react 4h, treat anti-
After should terminating, take out electrode, clean up, be dried；
D) by step C) dried electrode is placed in Muffle furnace, after calcining, is cooled to room temperature, i.e. prepares PCB101
(SC, MI)-TiO of molecular engram2NRs light anode.
Step B) in, in mixed solution, the molar concentration of titanium ion is that the molar concentration of 70mM, PCB101 is
5μM；The mass fraction of concentrated hydrochloric acid is 38wt%.
Step D) in, the treatment conditions of calcining are: calcining heat is 500 DEG C, and calcination time is 0.5h.
Actual sample is the sample mix liquid of test substance PCB101 and interfering material, in this sample mix liquid, treats
Survey the concentration of Substance P CB101 and interfering material ratio for 1:100.
In the present embodiment, interfering material is PCB126.
Embodiment 6
A kind of based single crystal TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, the method is with Polychlorinated biphenyls
101 (PCB101) are detection object, specifically include following steps:
1) prepare the standard solution of the test substance PCB101 of a series of variable concentrations, and be added separately to successively
As electrolyte in electrolyzer, it is sufficiently stirred for, stands；
2) use current versus time curve method, under ultraviolet light irradiates, be biased 0.8V, measure (SC,
MI)-TiO2NRs light anode photocurrent response in the PCB101 standard solution of variable concentrations, and according to photoelectricity
Stream and the relation drawing curve of concentration of standard solution；
3) preparation actual sample, and join as electrolyte in electrolyzer, it is sufficiently stirred for, stands；
4) under ultraviolet light irradiates, it is biased 0.8V, measures (SC, MI)-TiO2NRs light anode is at actual sample
Photocurrent response in product, and according to working curve I/I0=0.862+0.059lgC (unit: C, pM) calculates reality
The concentration of sample, wherein, I is (SC, MI)-TiO2NRs light anode photocurrent response in actual sample, I0
For (SC, MI)-TiO2NRs light anode photocurrent response in blank solution, then changed by the concentration of actual sample
Calculate the concentration obtaining test substance PCB101.
Described (SC, MI)-TiO2The preparation method of NRs light anode specifically includes following steps:
A) sol-gel process is used to grow one layer of TiO on FTO basal electrode2Crystal seed；
B) be 1:1 by volume by deionized water and concentrated hydrochloric acid mix and blend, then be simultaneously added dropwise butyl titanate and
PCB101, stirs, and prepares mixed solution；
C) first by step A) prepared growth has one layer of TiO2The FTO basal electrode of crystal seed is placed in reaction under high pressure
In still, add step B) prepared mixed solution, seal, and under the conditions of 140 DEG C, react 6h, treat anti-
After should terminating, take out electrode, clean up, be dried；
D) by step C) dried electrode is placed in Muffle furnace, after calcining, is cooled to room temperature, i.e. prepares PCB101
(SC, MI)-TiO of molecular engram2NRs light anode.
Step B) in, in mixed solution, the molar concentration of titanium ion is that the molar concentration of 35mM, PCB101 is
1μM；The mass fraction of concentrated hydrochloric acid is 38wt%.
Step D) in, the treatment conditions of calcining are: calcining heat is 400 DEG C, and calcination time is 2h.
Actual sample is the sample mix liquid of test substance PCB101 and interfering material, in this sample mix liquid, treats
Survey the concentration of Substance P CB101 and interfering material ratio for 1:100.
In the present embodiment, interfering material is PCB77.
Embodiment 7
A kind of based single crystal TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, the method is with Polychlorinated biphenyls
101 (PCB101) are detection object, specifically include following steps:
1) prepare the standard solution of the test substance PCB101 of a series of variable concentrations, and be added separately to successively
As electrolyte in electrolyzer, it is sufficiently stirred for, stands；
2) use current versus time curve method, under ultraviolet light irradiates, be biased 0.7V, measure (SC,
MI)-TiO2NRs light anode photocurrent response in the PCB101 standard solution of variable concentrations, and according to photoelectricity
Stream and the relation drawing curve of concentration of standard solution；
3) preparation actual sample, and join as electrolyte in electrolyzer, it is sufficiently stirred for, stands；
4) under ultraviolet light irradiates, it is biased 0.7V, measures (SC, MI)-TiO2NRs light anode is at actual sample
Photocurrent response in product, and according to working curve I/I0=0.862+0.059lgC (unit: C, pM) calculates reality
The concentration of sample, wherein, I is (SC, MI)-TiO2NRs light anode photocurrent response in actual sample, I0
For (SC, MI)-TiO2NRs light anode photocurrent response in blank solution, then changed by the concentration of actual sample
Calculate the concentration obtaining test substance PCB101.
Described (SC, MI)-TiO2The preparation method of NRs light anode specifically includes following steps:
A) sol-gel process is used to grow one layer of TiO on FTO basal electrode2Crystal seed；
B) be 1:1 by volume by deionized water and concentrated hydrochloric acid mix and blend, then be simultaneously added dropwise butyl titanate and
PCB101, stirs, and prepares mixed solution；
C) first by step A) prepared growth has one layer of TiO2The FTO basal electrode of crystal seed is placed in reaction under high pressure
In still, add step B) prepared mixed solution, seal, and under the conditions of 148 DEG C, react 5h, treat anti-
After should terminating, take out electrode, clean up, be dried；
D) by step C) dried electrode is placed in Muffle furnace, after calcining, is cooled to room temperature, i.e. prepares PCB101
(SC, MI)-TiO of molecular engram2NRs light anode.
Step B) in, in mixed solution, the molar concentration of titanium ion is that the molar concentration of 40mM, PCB101 is
2 μMs, the mass fraction of concentrated hydrochloric acid is 38wt%.
Step D) in, the treatment conditions of calcining are: calcining heat is 460 DEG C, and calcination time is 1.5h.
Actual sample is the sample mix liquid of test substance PCB101 and interfering material, in this sample mix liquid, treats
Survey the concentration of Substance P CB101 and interfering material ratio for 1:100.
In the present embodiment, interfering material is 2,4-D.
Embodiment 8
A kind of based single crystal TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, the method is with Polychlorinated biphenyls
101 (PCB101) are detection object, specifically include following steps:
1) prepare the standard solution of the test substance PCB101 of a series of variable concentrations, and be added separately to successively
As electrolyte in electrolyzer, it is sufficiently stirred for, stands；
2) use current versus time curve method, under ultraviolet light irradiates, be biased 0.6V, measure (SC,
MI)-TiO2NRs light anode photocurrent response in the PCB101 standard solution of variable concentrations, and according to photoelectricity
Stream and the relation drawing curve of concentration of standard solution；
3) preparation actual sample, and join as electrolyte in electrolyzer, it is sufficiently stirred for, stands；
4) under ultraviolet light irradiates, it is biased 0.6V, measures (SC, MI)-TiO2NRs light anode is at actual sample
Photocurrent response in product, and according to working curve I/I0=0.862+0.059lgC (unit: C, pM) calculates reality
The concentration of sample, wherein, I is (SC, MI)-TiO2NRs light anode photocurrent response in actual sample, I0
For (SC, MI)-TiO2NRs light anode photocurrent response in blank solution, then changed by the concentration of actual sample
Calculate the concentration obtaining test substance PCB101.
Described (SC, MI)-TiO2The preparation method of NRs light anode specifically includes following steps:
A) sol-gel process is used to grow one layer of TiO on FTO basal electrode2Crystal seed；
B) be 1:1 by volume by deionized water and concentrated hydrochloric acid mix and blend, then be simultaneously added dropwise butyl titanate and
PCB101, stirs, and prepares mixed solution；
C) first by step A) prepared growth has one layer of TiO2The FTO basal electrode of crystal seed is placed in reaction under high pressure
In still, add step B) prepared mixed solution, seal, and under the conditions of 152 DEG C, react 3h, treat anti-
After should terminating, take out electrode, clean up, be dried；
D) by step C) dried electrode is placed in Muffle furnace, after calcining, is cooled to room temperature, i.e. prepares PCB101
(SC, MI)-TiO of molecular engram2NRs light anode.
Step B) in, in mixed solution, the molar concentration of titanium ion is that the molar concentration of 45mM, PCB101 is
3 μMs, the mass fraction of concentrated hydrochloric acid is 38wt%.
Step D) in, the treatment conditions of calcining are: calcining heat is 480 DEG C, and calcination time is 1h.
Actual sample is the sample mix liquid of test substance PCB101 and interfering material, in this sample mix liquid, treats
Survey the concentration of Substance P CB101 and interfering material ratio for 1:100.
In the present embodiment, interfering material is G-30027.
Claims (9)
1. a based single crystal TiO2The Polychlorinated biphenyls photoelectrochemical assay method of nanometer rods, it is characterised in that should
Method, with PCB101 for detection object, specifically includes following steps:
1) prepare the standard solution of the test substance PCB101 of a series of variable concentrations, and be added separately to successively
As electrolyte in electrolyzer, it is sufficiently stirred for, stands；
2) use current versus time curve method, under ultraviolet light irradiates, be biased, measure (SC, MI)-TiO2
NRs light anode photocurrent response in the PCB101 standard solution of variable concentrations, and according to photoelectric current and standard
The relation drawing curve of solution concentration；
3) preparation actual sample, and join as electrolyte in electrolyzer, it is sufficiently stirred for, stands；
4) under ultraviolet light irradiates, it is biased, measures (SC, MI)-TiO2NRs light anode is in actual sample
Photocurrent response, and according to working curve I/I0The concentration of=0.862+0.059lgC calculating actual sample, wherein,
I is (SC, MI)-TiO2NRs light anode photocurrent response in actual sample, I0For (SC, MI)-TiO2NRs
Light anode photocurrent response in blank solution, then obtained test substance by the concentration conversion of actual sample
The concentration of PCB101.
A kind of based single crystal TiO the most according to claim 12The Polychlorinated biphenyls photoelectrochemical assay of nanometer rods
Method, it is characterised in that described (SC, MI)-TiO2The preparation method of NRs light anode specifically includes following step
Rapid:
A) sol-gel process is used to grow one layer of TiO on FTO basal electrode2Crystal seed；
B) be 1:1 by volume by deionized water and concentrated hydrochloric acid mix and blend, then be simultaneously added dropwise butyl titanate and
PCB101, stirs, and prepares mixed solution；
C) first by step A) prepared growth has one layer of TiO2The FTO basal electrode of crystal seed is placed in reaction under high pressure
In still, add step B) prepared mixed solution, seal, and under the conditions of 140-160 DEG C, react 2-6h,
After question response terminates, take out electrode, clean up, be dried；
D) by step C) dried electrode is placed in Muffle furnace, after calcining, is cooled to room temperature, i.e. prepares PCB101
(SC, MI)-TiO of molecular engram2NRs light anode.
A kind of based single crystal TiO the most according to claim 22The Polychlorinated biphenyls photoelectrochemical assay of nanometer rods
Method, it is characterised in that step B) described in mixed solution in, the molar concentration of titanium ion is 35-70mM.
A kind of based single crystal TiO the most according to claim 22The Polychlorinated biphenyls photoelectrochemical assay of nanometer rods
Method, it is characterised in that step B) described in mixed solution in, the molar concentration of PCB101 is 1-5 μM.
A kind of based single crystal TiO the most according to claim 22The Polychlorinated biphenyls photoelectrochemical assay of nanometer rods
Method, it is characterised in that step D) described in the treatment conditions of calcining be: calcining heat is 400-500 DEG C,
Calcination time is 0.5-2h.
A kind of based single crystal TiO the most according to claim 12The Polychlorinated biphenyls photoelectrochemical assay of nanometer rods
Method, it is characterised in that described bias is 0.6-0.8V.
A kind of based single crystal TiO the most according to claim 12The Polychlorinated biphenyls photoelectrochemical assay of nanometer rods
Method, it is characterised in that described actual sample is the sample mix liquid of test substance PCB101 and interfering material.
A kind of based single crystal TiO the most according to claim 72The Polychlorinated biphenyls photoelectrochemical assay of nanometer rods
Method, it is characterised in that in described sample mix liquid, the concentration ratio of test substance PCB101 and interfering material
For 1:100.
9. according to a kind of based single crystal TiO described in claim 7 or 82The Polychlorinated biphenyls Optical Electro-Chemistry of nanometer rods
Analysis method, it is characterised in that described interfering material include PCB126, PCB77, naphthalene, pyrene, 2,4-D,
One in G-30027 or bisphenol-A.
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