CN103175875A - Photoelectric chemical analysis method of polycyclic aromatic hydrocarbons with in situ molecular imprinting modified electrode - Google Patents
Photoelectric chemical analysis method of polycyclic aromatic hydrocarbons with in situ molecular imprinting modified electrode Download PDFInfo
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Abstract
The invention relates to a photoelectric chemical analysis method of polycyclic aromatic hydrocarbons with an in situ molecular imprinting modified electrode. The method comprises a method for preparing a ZnONRs@TiO2NTs based on molecular imprinting functionalization and a high-selectivity and high-sensitivity detection method of polycyclic aromatic hydrocarbons (PAHs) by adopting the modified electrode. Compared with the prior art, the photoelectric chemical analysis method adopts the in situ molecular imprinting ZnONRs as the selective recognition element and obtains single crystal molecular imprinting type ZnONRs on TiO2NTs, and thereby having an excellent imprinting effect; and the imprinting molecule PAHs has a conjugated structure which is advantageous for enhancing the photoelectric property of the electrode. Under irradiation of ultraviolet light, different PAHs can be selectively detected; the detection limit to PAHs such as naphthalene and pyrene reaches the order of magnitude of 10-9 mol.L-1; and the electrode is stable and has excellent reproducibility.
Description
Technical field
The present invention relates to belong to nano material, Optical Electro-Chemistry analysis and environmental monitoring technology field, especially relate to a kind of Optical Electro-Chemistry analytical approach of original position molecular imprinting modification electrode pair palycyclic aromatic.
Background technology
Palycyclic aromatic (Polycyclic Aromatic Hydrocarbons, PAHs) be that a class has the compound that two or more aromatic rings close-packed arrays form, they produce during generally by rough burnings such as coal, oil, timber, tobacco and organic high molecular compounds, be distributed widely in atmosphere, soil, river, seawater and food, and quite a few all has carcinogenesis.Monitoring and the quantitative analysis method of therefore, setting up a kind of highly sensitive high selectivity have important Significance for Environment.The current methods such as biochemical analysis that the detection of PAHs is mainly concentrated on gas chromatography, gas chromatography mass spectrometry isochromatic spectrum method and works out according to its mechanism of carcinogenesis.But these detection method instrument costlinesses, complicated operation, sample usually needs loaded down with trivial details pre-service etc., and the real-time online that is not suitable for very much PAHs in environment detects.
Electrochemical method be a kind of easy and simple to handle, respond technology quick, highly sensitive, that be easy to on-line monitoring.Yet, as a kind of non-electrochemical active substance, PAHs can't adopt direct electrochemical method to be detected, normally adopt the bioactivator modified electrode to measure, this has had a strong impact on stability and the reappearance of electrochemical analysis.And the Optical Electro-Chemistry analytical approach not only can take full advantage of the advantage on the 26S Proteasome Structure and Function of semiconductor excellence, more can utilize its PhotoelectrocatalytiPerformance Performance, catalytic oxidation non-electrochemical active substance, successfully overcome this defect of galvanochemistry.Because PAHs itself has large conjugated structure, compound with semiconductor after, contribute to improve the electric conductivity of electrode, show as the reducing of electrochemical impedance (EIS) of illumination condition bottom electrode; And semi-conductive photohole can move to the LOMO track of PAHs, promote the right separation in light induced electron-hole, and then improved semi-conductive photoelectrochemical behaviour, show as the increase of photocurrent on the i-t curve.Utilize this principle can realize quick, the highly sensitive photoelectric analysis to PAHs.
Molecular imprinting (Molecular imprinted technique, MIT) be a kind of method of modifying that makes electrode there is selectivity identification, there is good stability, the recognition capability advantages of higher, the normal macromolecular material that adopts carries out finishing to electrode, the original position molecular engram is to form in the preparation process of electrode material, and the present invention selects inorganic semiconductor metal oxide ZnO nanorod (NRs) as imprinted material, TiO
2nanotube (NTs), as base material, is characterized in: ZnO has good chemical stability, and grafting is at base material TiO
2there is good Photoelectrochemical stabilization after NTs is upper, and material preparation method is simply controlled.Be applied to construct the photoelectric sensing electrode of PAHs, and set up highly sensitive, selective light electricity analytical method to PAHs, there is important potential using value aspect the environmental monitoring of PAHs.
Summary of the invention
Purpose of the present invention is exactly the Optical Electro-Chemistry analytical approach that a kind of highly sensitive, high selectivity, a kind of original position molecular imprinting modification electrode pair palycyclic aromatic easily and fast are provided in order to overcome the defect that above-mentioned prior art exists, introducing the original position molecular imprinting makes this modified electrode have good molecule distinguishability, electrode structure is controlled and the molecular characterization of PAHs own has strengthened again the photoelectric analysis sensitivity of electrode, and has shown good reappearance and stability.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of Optical Electro-Chemistry analytical approach of original position molecular imprinting modification electrode pair palycyclic aromatic, concrete steps are as follows:
(1) TiO
2the preparation of NTs electrode:
Using the titanium sheet as substrate, pure titanium sheet is used to 80 successively
#, 320
#with 500
#after sand papering, use abrasive paper for metallograph to carry out polishing to its surface, make its surface smoothing, follow difference ultrasonic cleaning 15 ~ 20min in distilled water and acetone, then rinse well with redistilled water; Then by titanium sheet micro-etching 10 ~ 15min that boils of water-bath in the concentrated hydrochloric acid of 1:1 dilution, at room temperature using the titanium sheet as anode again, and the Pt plate electrode, as negative electrode, maintains electrode separation 1cm, in containing the aqueous solution of 3 ~ 5wt%HF under magnetic agitation, constant potential 20 ~ 30V anode pre-oxidation 1h; The titanium sheet is taken out, rinse well and air drying after, be placed in and contain 0.25wt%NH
4f, 1wt%H
2in the ethylene glycol solution of O, constant potential 20 ~ 30V anodic oxidation 2 ~ 3h under magnetic agitation is etched into TiO in the Ti substrate
2nanotube.Taking-up is etched with TiO
2the Ti substrate of nanotube, with after redistilled water ultrasonic cleaning drying, is placed in tubular furnace at 450 ~ 500 ℃ of thermal treatment 3 ~ 5h of oxygen atmosphere, prepares the TiO of stable growth in the Ti substrate
2nanotube; Be TiO
2nTs.
(2) preparation work electrode: adopt the method for induce-Hydrothermal Synthesis of crystal seed, at first use the method for sol-gel by certain density Zn (CH
3cOO)
2ethanolic solution is spin-coated on the TiO that step (1) obtains
2the NTs substrate surface, the each first rotation of the rotating speed with 100 ~ 300rpm 3s, then, with 3000rpm rotation 10 ~ 20s, repeat altogether 8 ~ 10 times.Then in muffle furnace, face up, 350 ~ 400 ℃ of pyrolysis 0.5 ~ 1h, obtain the ZnO crystal seed layer.Then front side of matrix is placed on downwards in the autoclave of Teflon liner, immersing composition is 0.02mol L
-1zn (NO
3)
2, 0.02mol L
-1(CH
2)
6n
4with 0.4 ~ 1mmol L
-1in the precursor solution of microsphere, react 3 ~ 7h under 80 ~ 90 ℃.Wash and air drying with deionized water after taking out electrode, under magnetic agitation, replace cleaning electrode and so repeat 3 times with the removal microsphere with ethanol and acetone respectively, obtain the ZnO NRsTiO of original position PAHs molecular engram after air drying
2the NTs electrode.
(3) select different types of PAHs as detected object, by the 0.1M Na of the PAHs of a series of variable concentrations of preparation
2sO
4standard solution joins respectively in electrolytic cell successively as electrolytic solution, with the ZnO NRsTiO of prepared molecular engram
2the NTs electrode is working electrode, after stirring 10 minutes, standing; Adopt the method for i-t curve, under UV-irradiation, apply bias voltage 0.6V, measure photocurrent, linear relationship drawing curve according to photocurrent and concentration of standard solution, after each mensuration, the working electrode in electrolytic cell is replaced to agitator treating 3 times in ethanol and acetone, remove the microsphere of absorption, realize regeneration and the renewal of electrode surface.
In the present invention, palycyclic aromatic naphthalene and the pyrene of described PAHs for often coexisting with gaseous state, have respectively two aromatic rings and four aromatic rings.
The described original position molecular engram of employing of the present invention ZnO NRsTiO
2the Optical Electro-Chemistry analytical approach of NTs electrode, will contain the 0.1M Na of blotting molecule or testing molecule and interfering material (PAHs of different number of rings)
2sO
4solution, as electrolyte solution, stirs 10min and is beneficial to the selective enrichment of testing molecule at electrode surface, opens ultraviolet source after essence; Select the method for i-t curve, under the condition that applies bias voltage (0.6V (Vs. SCE)), measure photocurrent.Size by photocurrent is carried out quantitatively PAHs.After test finishes, modified electrode is alternately cleaned with ethanol and acetone respectively and so repeats 3 times to remove microsphere under magnetic agitation, then air drying, make renewal of electrode surface and regeneration.Its characteristics are, experimental implementation is simple, and the selectivity of electrode is good, highly sensitive, has good stability, and long service life is reusable, and stable Optical Electro-Chemistry signal is arranged.
Compared with prior art, the present invention has advantages of following:
(1) adopt first the method for Optical Electro-Chemistry to detect PAHs, because PAHs itself does not have electrochemical activity, and its large conjugated structure makes the LOMO orbital energy lower, transportable photohole, improve the photoelectrochemical behaviour of photocatalyst, therefore, Optical Electro-Chemistry is a kind of desirable PAHs analysis means.
(2) adopt crystal seed to induce hydrothermal synthesis method to prepare original position molecular engram single crystal ZnO NRs, experimental implementation is comparatively simple, microsphere PAHs growth together thereupon in the process formed at ZnO NRs, trace is on the ZnO NRs with monocrystalline hexagonal prism structure, and crystal defect is less, and the selectivity recognition capability of removing the microsphere rear electrode is higher, selectivity is good, and the trace quality is higher, the ZnO electrode prepared with sol-gel process is compared, and sensitivity is better.
(3) the semiconductor combination electrode prepared, by forming heterojunction and apply certain bias voltage in testing process, has promoted the light induced electron of electrode and separating of hole, has suppressed the photoetch of ZnO; Microsphere PAHs has also suppressed the ZnO photoetch because having moved away photohole in the photoelectrochemical behaviour of intensifier electrode, makes electrode have good stability and reappearance.
(4) Optical Electro-Chemistry detection method of the present invention has realized the detection of the environmental contaminants PAHs of non-electrochemical activity, and the Optical Electro-Chemistry instrument cheapness of employing is portable, and method is simple, and has higher sensitivity, and detectability can reach 10
-9mol/L.
The accompanying drawing explanation
Fig. 1 is naphthalene trace ZnO NRsTiO prepared by described employing original position molecular engram
2the scanning electron microscope diagram of NTs electrode.
Fig. 2 is described naphthalene trace ZnO NRsTiO
2the SEAD figure of NTs electrode.
The photocurrent that Fig. 3 is naphthalene trace electrode is with the photocurrent variations curve of pyrene solution concentration.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The ZnO NRsTiO used in the present invention
2the NTs electrode be with reference to Lei Yanzhu etc. at document (Fabrication, Characterization, and Photoelectrocatalytic Application of ZnO Nanorods Grafted on Vertically Aligned TiO2 Nanotubes, Lei Yanzhu, Zhao Guohua et al, J. Phys. Chem. C, 2009, 113, 19067-19076), the crystal seed of report induces hydrothermal synthesis method to prepare gained, and carried out corresponding improvement, specifically by the Ti sheet of having polished at first in the concentrated hydrochloric acid of 1:1 dilution in 85 ℃ of etching 15min, then using it as anode under 25 ℃ of constant temperature, the Pt plate electrode is as negative electrode, maintain electrode separation 1cm, in containing the aqueous solution of 5wt%HF under magnetic agitation, constant potential 20V anode pre-oxidation 1h.Electrode is taken out, rinse well and air drying after, be placed in and contain 0.25wt%NH
4f, 1wt%H
2in the ethylene glycol solution of O, constant potential 20V anodic oxidation 2h under magnetic agitation is etched into TiO in the Ti substrate
2nanotube.With after redistilled water ultrasonic cleaning 5min drying, be placed in tubular furnace at 500 ℃ of thermal treatment 3h of oxygen atmosphere after the taking-up electrode, intensification and rate of temperature fall are 5 ℃ of min
-1.Prepare the TiO of stable growth in the Ti substrate
2nanotube (TiO
2nTs).
At the TiO that adopts said method to prepare
2nTs is upper, uses the method for sol-gel by 5mmol L
-1zn (CH
3cOO)
2ethanolic solution is spin-coated on the TiO of preparation
2the NTs substrate surface, the each first rotation of the rotating speed with 100rpm 3s, then, with 3000rpm rotation 10s, repeat altogether 10 times.Then in muffle furnace, face up, 350 ℃ of pyrolysis 0.5h, obtain the ZnO crystal seed layer.Then front side of matrix is placed on downwards in the autoclave of Teflon liner, immersing composition is 0.02mol L
-1zn (NO
3)
2, 0.02mol L
-1(CH
2)
6n
4with 1mmol L
-1the precursor solution of naphthalene in, react 5h under 90 ℃.Wash and air drying with deionized water after taking out electrode, then under magnetic agitation, replace cleaning electrode and so repeat 3 times with the removal microsphere with ethanol and acetone respectively, obtain respectively original position naphthalene trace ZnO NRsTiO after air drying
2the NTs electrode, how the scanning electron microscope diagram of trace electrode is as shown in schematic diagram 1 for it, and SEAD figure is as shown in Figure 2.
The preparation of pyrene trace electrode adopts method similar to Example 1, and slightly change, specifically by the Ti sheet at first in the concentrated hydrochloric acid of 1:1 dilution in 90 ℃ of etching 10min, then using it as anode under 25 ℃ of constant temperature, the Pt plate electrode is as negative electrode, maintain electrode separation 1cm, in containing the aqueous solution of 3wt%HF under magnetic agitation, constant potential 20V anode pre-oxidation 1h.Electrode is taken out, rinse well and air drying after, be placed in and contain 0.25wt%NH
4f, 1wt%H
2in the ethylene glycol solution of O, constant potential 20V anodic oxidation 3h under magnetic agitation is etched into TiO in the Ti substrate
2nanotube.With after redistilled water ultrasonic cleaning 10min drying, be placed in tubular furnace at 500 ℃ of thermal treatment 3h of oxygen atmosphere after the taking-up electrode, intensification and rate of temperature fall are 3 ℃ of min
-1.Prepare the TiO of stable growth in the Ti substrate
2nanotube (TiO
2nTs).
At the TiO that adopts said method to prepare
2nTs is upper, uses the method for sol-gel by saturated Zn (CH
3cOO)
2ethanolic solution is spin-coated on the TiO of preparation
2the NTs substrate surface, the each first rotation of the rotating speed with 100rpm 3s, then, with 3000rpm rotation 15s, repeat altogether 10 times.Then in muffle furnace, face up, 350 ℃ of pyrolysis 45min, obtain the ZnO crystal seed layer.Then front side of matrix is placed on downwards in the autoclave of Teflon liner, immersing composition is 0.02mol L
-1zn (NO
3)
2, 0.02mol L
-1(CH
2)
6n
4with 0.5mmol L
-1the precursor solution of pyrene in, react 5h under 85 ℃.Wash and air drying with deionized water after taking out electrode, then under magnetic agitation, replace cleaning electrode and so repeat 3 times with the removal microsphere with ethanol and acetone respectively, obtain respectively original position pyrene trace ZnO NRsTiO after air drying
2the NTs electrode.
Embodiment 3
Adopt the Na of 0.1M
2sO
4solution is electrolyte solution, prepares the naphthalene standard solution of a series of variable concentrations.Original position naphthalene trace ZnO NRsTiO with preparation in embodiment 1
2the NTs electrode is working electrode, and the Pt electrode is to electrode, and saturated calomel electrode (SCE) is contrast electrode, open ultraviolet source, set the current potential that applies of 0.6V (Vs. SCE), utilize electrochemical workstation CHI660C to adopt the method for i-t curve, measure photocurrent, and pass through computer recording.First measure the photocurrent of electrode in blank electrolysis matter solution, then measure the photocurrent add after variable concentrations naphthalene titer, used working electrode replaces cleaning electrode and so repeats 3 times to remove the microspheres of absorption at ethanol and acetone.Linear relationship drawing curve according to naphthalene concentration with corresponding photocurrent, the detectability of naphthalene can reach 5 * 10
-9molL
-1, photocurrent with the change curve of concentration as shown in Figure 3.
Embodiment 4
Similar, the Na of employing 0.1M
2sO
4solution is electrolyte solution, prepares the pyrene standard solution of a series of variable concentrations, with the original position pyrene trace ZnO NRsTiO of embodiment 2 preparations
2the NTs electrode is working electrode, utilize electrochemical workstation to adopt the method for i-t curve to measure the change curve of its photocurrent with concentration, used working electrode replaces cleaning electrode and so repeats 3 times to remove the microsphere of absorption at ethanol and acetone, then according to the linear relationship drawing curve of pyrene concentration and corresponding light electric current, the detectability of pyrene can reach 1.25 * 10
-9m.
Embodiment 5
At first, described in embodiment 2, the working electrode of used pyrene trace is replaced to cleaning electrode and so repeats 3 times to remove the microsphere of absorption at ethanol and acetone, realize surperficial renewal and regeneration, then to contain finite concentration pyrene or pyrene and 20 times of concentration in the interfering material of pyrene, as the mixed solution of benzene, naphthalene is electrolytic solution, the same three-electrode system that adopts, measure corresponding photocurrent on the CHI660C electrochemical workstation, and the concentration of pyrene in the real solution calculated according to the working curve of drawing in embodiment 2.Result shows, after adding chaff interference, photocurrent has increase to a certain degree, but the impact of the photocurrent of the detection of pyrene all is less than to 7%, and this has embodied the prepared good selectivity analysis ability of pyrene Nanosilica electrode.
Claims (2)
1. the Optical Electro-Chemistry analytical approach of an original position molecular imprinting modification electrode pair palycyclic aromatic is characterized in that concrete steps are as follows:
(1) TiO
2the preparation of NTs electrode:
Using the titanium sheet as substrate, pure titanium sheet is used to 80 successively
#, 320
#with 500
#after sand papering, use abrasive paper for metallograph to carry out polishing to its surface, make its surface smoothing, follow difference ultrasonic cleaning 15 ~ 20min in distilled water and acetone, then rinse well with redistilled water; Then by titanium sheet micro-etching 10 ~ 15min that boils of water-bath in the concentrated hydrochloric acid of 1:1 dilution, at room temperature using the titanium sheet as anode again, and the Pt plate electrode, as negative electrode, maintains electrode separation 1cm, in containing the aqueous solution of 3 ~ 5wt%HF under magnetic agitation, constant potential 20 ~ 30V anode pre-oxidation 1h; The titanium sheet is taken out, rinse well and air drying after, be placed in and contain 0.25wt%NH
4f, 1wt%H
2in the ethylene glycol solution of O, constant potential 20 ~ 30V anodic oxidation 2 ~ 3h under magnetic agitation is etched into TiO in the Ti substrate
2nanotube; Taking-up is etched with TiO
2the Ti substrate of nanotube, with after redistilled water ultrasonic cleaning drying, is placed in tubular furnace at 450 ~ 500 ℃ of thermal treatment 3 ~ 5h of oxygen atmosphere, prepares the TiO of stable growth in the Ti substrate
2nanotube; Be TiO
2nTs;
(2) preparation work electrode: adopt the method for induce-Hydrothermal Synthesis of crystal seed, at first use the method for sol-gel by certain density Zn (CH
3cOO)
2ethanolic solution is spin-coated on the TiO that step (1) obtains
2the NTs substrate surface, the each first rotation of the rotating speed with 100 ~ 300rpm 3s, then, with 3000rpm rotation 10 ~ 20s, repeat altogether 8 ~ 10 times; Then in muffle furnace, face up, 350 ~ 400 ℃ of pyrolysis 0.5 ~ 1h, obtain the ZnO crystal seed layer; Then front side of matrix is placed on downwards in the autoclave of Teflon liner, immersing composition is 0.02mol L
-1zn (NO
3)
2, 0.02mol L
-1(CH
2)
6n
4with 0.4 ~ 1mmol L
-1in the precursor solution of microsphere, react 3 ~ 7h under 80 ~ 90 ℃; Wash and air drying with deionized water after taking out electrode, under magnetic agitation, replace cleaning electrode and so repeat 3 times with the removal microsphere with ethanol and acetone respectively, obtain the ZnO NRsTiO of original position PAHs molecular engram after air drying
2the NTs electrode;
(3) select different types of PAHs as detected object, by the 0.1M Na of the PAHs of a series of variable concentrations of preparation
2sO
4standard solution joins respectively in electrolytic cell successively as electrolytic solution, with the ZnO NRsTiO of prepared molecular engram
2the NTs electrode is working electrode, after stirring 10 minutes, standing; Adopt the method for i-t curve, under UV-irradiation, apply bias voltage 0.6V, measure photocurrent, linear relationship drawing curve according to photocurrent and concentration of standard solution, after each mensuration, the working electrode in electrolytic cell is replaced to agitator treating 3 times in ethanol and acetone, remove the microsphere of absorption, realize regeneration and the renewal of electrode surface.
2. according to method claimed in claim 1, it is characterized in that palycyclic aromatic naphthalene and the pyrene of described PAHs for often coexisting with gaseous state, there are respectively two aromatic rings and four aromatic rings.
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| CN105158236A (en) * | 2015-08-03 | 2015-12-16 | 济南大学 | Preparation method of electrochemiluminescence sensor for detecting benzoapyrene |
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| CN105158236A (en) * | 2015-08-03 | 2015-12-16 | 济南大学 | Preparation method of electrochemiluminescence sensor for detecting benzoapyrene |
| CN106053558A (en) * | 2016-06-17 | 2016-10-26 | 同济大学 | Pd quantum dot-modified TiO2 nanorod-based photoelectric chemical analysis method and application thereof |
| CN106053558B (en) * | 2016-06-17 | 2019-01-25 | 同济大学 | TiO is modified based on Pd quantum dot2The photoelectrochemical assay method and its application of nanometer rods |
| CN106587282A (en) * | 2016-12-08 | 2017-04-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Difunctional multi-template molecularly imprinted type photoelectric anode material and preparation method and application |
| CN106587282B (en) * | 2016-12-08 | 2020-02-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Double-functional multi-template molecularly imprinted photoelectric anode material and preparation and application thereof |
| CN109580751A (en) * | 2018-12-03 | 2019-04-05 | 中国科学院烟台海岸带研究所 | A method of realizing that molecular imprinted polymer membrane ion selective electrode updates |
| CN110316795A (en) * | 2019-07-10 | 2019-10-11 | 同济大学 | A kind of electrochemical membrane component of selective removal pollutant and preparation method thereof |
| CN111007119A (en) * | 2019-12-27 | 2020-04-14 | 郑州轻工业大学 | Molecular imprinting modification TiO2nanotube-CdS quantum dot composite material, photoelectrochemical sensor, preparation method and application |
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