CN104914143B - A kind of molecular imprinting functionalization CdS/3DOM TiO in situ2The photoelectric analysis method of/BDD electrode pair BaPs - Google Patents
A kind of molecular imprinting functionalization CdS/3DOM TiO in situ2The photoelectric analysis method of/BDD electrode pair BaPs Download PDFInfo
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Abstract
The present invention relates to a kind of molecular imprinting functionalization CdS/3DOM TiO in situ2The photoelectric analysis method of/BDD electrode pair BaPs.First using hard template method combination sol-gal process in BDD surface construction 3DOM TiO2, the CdS nano-particles of BaP molecular imprinting functionalizations in situ are then assembled by SILAR method, CdS/3DOM TiO are constructed out2/ BDD optical electro-chemistry sensors.Catalytic species selection and microstructure of the present invention by photoelectric sensor are controlled, and can be achieved to detect the highly sensitive of BaP, high selectivity.The present invention uses original position molecular imprinting functionalization CdS nano-particles alternatively property recognition element, with more stable imprinted sites and selective power；TiO2Three-dimensional macroporous structure have higher space specific surface area, not only contribute to recognition element CdS uniform load, and can be with CdS formation hetero-junctions, while making electrode acquisition visible photoelectric respone ability, the separative efficiency of photo-generate electron-hole is improved, makes electrode that there is the visible light-responded of stability and high efficiency.Under visible light illumination, photoelectric analysis detection is carried out to the BaP in water sample using the sensing electrode, test limit reaches 10‑14mol·L‑1The order of magnitude.
Description
Technical field
The invention belongs to technical field of environmental detection, it is related to a kind of based on molecular imprinting functionalization CdS/3DOM in situ
TiO2/ BDD electrode pair BaPs（BaP）Photoelectrochemical assay method.
Background technology
BaP（BaP）It is a kind of common multiring aromatic hydrocarbon environmental contaminants, mainly by coal, oil, timber, You Jigao
The imperfect combustions such as molecular compound are produced, and are widely present in air, water body, soil and food, are first and are found
Environmental chemical carcinogen, is also carcinogenicity most strong one kind in polycyclic aromatic hydrocarbon, by as polycyclic aromatic hydrocarbons contaminated in monitoring of environmental
Important indicator.Therefore, carrying out highly sensitive high selectivity quantitative analysis to BaP has important Significance for Environment.
BaP traditional detection method mainly has spectral chromatography mass spectrum quasi-tradition instrument analytical method and biological immune sensing device
Alanysis method.The former has detection method ripe, the advantages of as a result accurate, but generally requires the large-scale instrument for using costliness
Device, sample pre-treatments are complicated, it is difficult to realize on-line checking；The latter is using biomolecule such as DNA, antibody antigens as identification member
Part, although with preferable selectivity, but the activity of biomolecule is easily influenceed by external environment such as temperature, pH etc.,
Cause the stability and reappearance of testing result poor.
Electrochemical analysis method be a kind of highly sensitive, fast-response, it is easy to operate, be easy to on-line monitoring analysis method, but
BaP is used as a kind of non-electroactive material, it is impossible to directly detected by electrochemical method, typically by biological in electrode over-assemble
Active material carries out indirect determination, but the introducing of biomolecule can reduce the stability and reappearance of electrochemical analysis.Photoelectricity
Chemical analysis method is that electrode is modified with conductor photocatalysis material, the change for the photocatalysis signal that analyte is triggered
Electrochemical signals are converted into, the detection for non-electroactive material is realized.There is BaP molecules many phenyl ring, class graphene to be total to
Yoke structure, the stable conjugatedπbond of intramolecular can promote electronics to conduct.Under illumination condition, the light that conductor photocatalysis material is produced
Raw electronics is quickly transferred to basal electrode by BaP, so as to improve the separative efficiency of photo-generate electron-hole, shows as photoelectric current
Increase.Utilize the signal intensity of photoelectric current, it is possible to achieve the analysis to BaP is detected.However, photoelectrochemical assay method does not have
Alternative identification function, it is therefore desirable to molecular recognition function is carried out to photoelectric analysis electrode, there is photoelectric analysis method
Selectivity.
Molecular imprinting technology be it is a kind of make electrode that there is the method for modifying of Selective recognition function by the shape-selective effect in space,
With good molecule distinguishability and stability.The present invention is carried out former using inorganic semiconductor CdS as molecular engram material
Position molecular imprinting functionalization, i.e., synchronize molecular engram in the synthesis of CdS nano-particles, obtain molecular imprinting functionalization in situ
CdS nano-particles.CdS is a kind of narrow-band semiconductor material of stabilization, and it moves body material TiO to broadband2It is compounded to form heterogeneous
Knot, is demonstrated by excellent visible light catalytic performance.Binding molecule engram technology, constructs the optical electro-chemistry sensor based on BaP, real
Now the highly sensitive of BaP, high selectivity detection to environmental pollutants.
The content of the invention
The purpose of the present invention is aiming at existing BaP（BaP）Not high, complex operation of sensitivity of detection technique etc. lacks
A kind of molecular imprinting functionalization CdS/3DOM TiO in situ for falling into and providing2The photoelectric analysis method of/BDD electrode pair BaPs.
The introducing of molecular imprinting technology in situ assigns the electrode good molecular recognition function；By choosing, excellent catalysis material is simultaneously
Its microstructure is controlled, the signal amplification of the electrode is realized, improves the sensitivity of photoelectric analysis.
The present invention proposes a kind of molecular imprinting functionalization CdS/3DOM TiO in situ2The photoelectricity of/BDD electrode pair BaPs
Analysis method, using hard template method-sol-gal process in BDD basal electrode surface-assembled 3DOM TiO2, pass through continuous ionic layer
Adsorption reaction method further loads BaP molecular imprinting functionalization CdS nano-particles in situ, prepares CdS/3DOM TiO2/
BDD optical electro-chemistry sensors, realize and detect that detection sensitivity reaches 10 to the highly sensitive of BaP, high selectivity-15 mol·L-1Number
Magnitude；Comprise the following steps that：
（1）The pretreatment of BDD electrodes：Using pending BDD electrodes as working electrode, platinum electrode is auxiliary electrode, is satisfied
It is reference electrode with calomel electrode, is placed in 1 ~ 2molL-1 H2SO4In solution, using -3 ~ 3V multisteps potentiometry cleaning 20 ~
30min, then takes out BDD electrodes, and is cleaned with deionized water, is subsequently placed at water-bath in chloroazotic acid and boils 10 ~ 20min, finally will
Electrode is cleaned by ultrasonic in deionized water, acetone, deionized water successively, after drying naturally, obtains the BDD electrodes of cleaning；
（2）3DOM TiO on BDD electrodes2Preparation：
(2.1) pretreated BDD electrodes are placed on by 0.1 ~ 0.5%wt using hard template method combination sol-gel process vertically
Polystyrene（PS）In microsphere suspension liquid, 40 ~ 60 DEG C of drying in baking oven are placed in, PS microballoons is uniformly assembled in BDD electrode tables
Face；
(2.2) TiO is prepared2Dense HCl, i.e., be added in butyl titanate by precursor solution, stirring, can while adding ethanol
Obtain TiO2Precursor solution, wherein：Dense HCl, butyl titanate and ethanol volume ratio are 1:2.5:6；
(2.3) the above-mentioned BDD electrodes for being assembled with PS microballoons are slowly immersed in TiO2In precursor solution, 20 ~ 50s is stood
Afterwards, BDD electrodes are slowly withdrawn with 1 ~ 3mm/s speed, be then placed within baking oven, dried 1 ~ 2 hour under the conditions of 50 ~ 80 DEG C；
(2.4) electrode for obtaining step (2.3), which is put in tube furnace, carries out two step calcination processings, and calcining heat is respectively
300 DEG C and 400 DEG C, it is 1 ~ 3h often to walk the calcining at constant temperature time, and heating rate is 2 ~ 5 DEG C/min, obtains 3DOM TiO2/ BDD electricity
Pole；
（3）The assembling of BaP original positions molecular imprinting functionalization CdS nano-particles：Will using SILAR method
Step（2）The 3DOM TiO of middle preparation2/ BDD electrodes immerse 0.02 ~ 0.06 molL successively-1 Cd(NO3)2Solution（Containing 0.1 ~
0.5mmol·L-1BaP）、0.02~0.06 mol·L-1 Na2S solution（Containing 0.1 ~ 0.5mmolL-1BaP）, deionized water 1,
In deionized water 2, a cycle period, 3DOM TiO are designated as2Dip time of/BDD the electrodes in each solution is 10 ~ 30s；
After circulation 10 ~ 20 cycles of dipping, electrode is taken out, is placed in tube furnace, in N2Under atmosphere carry out 400 ~ 500 DEG C calcining 2 ~
3h, heating rate is 2 ~ 5 DEG C/min.CdS/3DOM TiO are obtained after Temperature fall2/ BDD electrodes；
（4）BaP photoelectric analysis：Prepare 0.1 ~ 0.2 molL of BaP containing various concentrations a series of-1PBS（Containing 0.1 ~
0.2 mol·L-1AA, pH=7.0 ~ 8.0）Standard liquid is respectively as electrolyte, with prepared CdS/3DOM TiO2/BDD
Electrode sets up three-electrode system as working electrode, puts the electrodes into electrolyte, is stood after 5 ~ 10 min of stirring；Using meter
When current method, under visible light illumination, apply 0 ~ 0.3V bias, determine photoelectric current；Calculated by the work area of working electrode
Go out density of photocurrent, and according to density of photocurrent and the linear relationship drawing curve of concentration of standard solution；Determine every time
Working electrode is taken out after, alternate agitation is cleaned 2 ~ 5 times in ethanol and acetone, remove the microsphere of absorption, make electrode
Surface is regenerated and updated；
(5) CdS/3DOM TiO2The selective light electroanalysis of/BDD electrodes：Prepare respectively containing disturbance material
0.1~0.2 mol·L-1PBS（Containing 0.1 ~ 0.2 molL-1AA, pH=7.0 ~ 8.0）Solution, and respectively as electrolyte, with
Prepared CdS/3DOM TiO2/ BDD electrodes are as working electrode, using step（4）Methods described, determines electrode and exists respectively
Photoelectric current in disturbance thing solution, calculates density of photocurrent.Light of the comparison electrode in the BaP standard liquids of same concentrations
Current density, calculates jamming rate of each interfering material for BaP.Working electrode is taken out after the completion of determining every time, in ethanol
Cleaned 2 ~ 5 times with alternate agitation in acetone, remove the interfering material of absorption, electrode surface is regenerated and is updated.
In the present invention, the solution containing interfering material is by 5.0 × 10-12 mol·L-1Test substance BaP respectively with phase
With the BaP of concentration interfering material mixing, the selection performance of inspecting electrode.
In the present invention, the interfering material be coexisted to BaP, the polyaromatic hydrocarbon pollutant benzene that structure is similar, naphthalene,
Pyrene.
Compared with prior art, the present invention has advantages below：
（1）Molecular imprinting functionalization is carried out to CdS nano-particles using molecular imprinting technology in situ, in CdS nano-particles
Microsphere BaP syntrophisms therewith during formation, remove and retain BaP traces position after microsphere on CdS nano-particles
Point, compared to organic polymer blotting membrane, inorganic material rigidity imprinted sites Selective recognition ability is higher, can distinguish with
Polyaromatic hydrocarbon pollutant benzene that BaP coexists, that structure is similar, naphthalene, pyrene；In addition inorganic imprinted material is unlikely to deform or aging,
Sensitivity and stability are more preferable.
（2）Using narrow-band semiconductor CdS and broadband semiconductor TiO2It is compound so that the light absorbs band edge of electrode is to visible ray
Wave band red shift, realizes the visible light-responded of electrode.While TiO2Three-dimensional ordered macroporous structure there is larger space to compare surface
Product, makes CdS uniform loads in TiO2Skeleton structure on, and form heterogeneous nodule structure, effectively facilitate CdS light induced electrons and sky
The separation in cave, realizes that photosignal amplifies, the stability and reappearance of electrode are preferable.BDD is used as basal electrode material, background electricity
Stream is low, and chemistry, electrochemical stability are good, and the interference to analysis detection is small, can improve the degree of accuracy and the precision of detection.
（3）Detect that BaP, BaP do not have electro-chemical activity, its molecular conjugation pi bond in itself using photoelectrochemical assay method
Structure has the ability that class graphene conducts electronics, and the photoelectrochemical behaviour of photochemical catalyst can be improved by being combined with photochemical catalyst, leads to
The photoelectric respone signal intensity of photochemical catalyst is crossed, BaP quantitative analyses are realized, more traditional chromatographic mass spectrometry alanysis method has operation
Convenient, response is rapid sensitive, and selectivity is good, can the advantage such as on-line checking, compared with biology sensor have higher stability and
Reappearance.
Brief description of the drawings
Fig. 1 is described use BaP original positions molecular imprinting functionalization CdS/3DOM TiO2The scanning electron of/BDD electrodes shows
Micro mirror figure.
Fig. 2 is described BaP original positions molecular imprinting functionalization CdS/3DOM TiO2The density of photocurrent of/BDD electrodes with
The variation diagram of BaP solution concentrations.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
One kind is based on original position molecular imprinting functionalization CdS/3DOM TiO2/ BDD electrode pairs BaP photoelectrochemical assay side
Method, electrode is constructed by following steps and obtained：
1）The pretreatment of BDD electrodes：
Using pending BDD electrodes as working electrode, platinum electrode is auxiliary electrode, and saturated calomel electrode is reference electricity
Pole, is placed in 1molL-1 H2SO4In solution, using multistep potentiometry（- 3.5V, 10s；3.5V, 10s）30min is cleaned, then
Take out BDD electrodes, and cleaned with deionized water, be subsequently placed at water-bath in chloroazotic acid and boil 15min, finally by electrode successively go from
It is cleaned by ultrasonic 3min in sub- water, acetone, deionized water, after drying naturally, obtains the BDD electrodes of cleaning.
2）3DOM TiO2Preparation
Pretreated BDD electrodes are placed on to 0.1%wt polyphenyl second vertically using hard template method combination sol-gel process
Alkene（PS）In microsphere suspension liquid, 40 DEG C of drying in baking oven are placed in, PS microballoons is uniformly assembled in BDD electrode surfaces.Then prepare
TiO2The dense HCl of certain volume, i.e., be added in butyl titanate by precursor solution, stirring, while adding ethanol can obtain, it is dense
HCl, butyl titanate and ethanol volume ratio are 1:2.5:6.The above-mentioned BDD electrodes for being assembled with PS microballoons are slowly immersed in above-mentioned
TiO2In precursor solution, electrode is slowly withdrawn with 1mm/s speed after standing 30s, is then placed within baking oven, 60 DEG C of bars
Dried 1 hour under part.Above-mentioned electrode is put in tube furnace and carries out two step calcinings, calcining heat is respectively 300 DEG C and 400 DEG C,
Often the step calcining at constant temperature time is 2h, and heating rate is 2 DEG C/min, obtains 3DOM TiO after Temperature fall2/ BDD electrodes.
3）The assembling of BaP original positions molecular imprinting functionalization CdS nano-particles
Will using SILAR method（2）The electrode of middle preparation immerses 0.05 molL successively-1 Cd
(NO3)2Solution（Containing 0.1mmolL-1BaP）、0.05 mol·L-1 Na2S solution（Containing 0.1mmolL-1BaP）, deionized water
1st, in deionized water 2, a cycle period is designated as, dip time of the electrode in each solution is 30s.Circulation 15 week of dipping
After phase, electrode is taken out, is placed in tube furnace, in N2500 DEG C of calcining 2h are carried out under atmosphere, heating rate is 5 DEG C/min.It is natural
BaP original positions molecular imprinting functionalization CdS/3DOM TiO are obtained after cooling2/ BDD electrodes.
BaP original positions molecular imprinting functionalization CdS/3DOM TiO2The pattern of/BDD electrodes is aobvious by Flied emission scanning electron
Micro mirror（SEM）Characterized, see Fig. 1, it can be seen that BDD surfaces successfully assemble pattern clearly 3DOM TiO2,
The CdS nano-particle uniform loads of BaP molecular imprinting functionalizations are in TiO2Three-dimensional ordered macroporous skeleton above.
Embodiment 2
Prepare a series of BaP of various concentrations 0.1 molL-1PBS（Containing 0.1 molL-1AA, PH=7.4）Mark
Quasi- solution is added separately in electrolytic cell as electrolyte, with BaP prepared in embodiment 1 molecular imprinting functionalizations in situ
CdS/3DOM TiO2/ BDD electrodes are as working electrode, and platinum electrode is used as reference electricity as auxiliary electrode, saturated calomel electrode
Pole, above-mentioned three-electrode system is placed in electrolyte and stirs standing after 5min.Using electrochemical workstation CHI660C, using meter
When current method, under visible light illumination, apply 0V bias, determine photoelectric current.Determine electrode respectively first molten in blank electrolysis matter
The molL of liquid 0.1-1PBS（Containing 0.1 molL-1AA, PH=7.4）With the photoelectricity after addition various concentrations BaP standard liquids
Stream, then converses density of photocurrent according to the work area of electrode.Finally according to density of photocurrent and BaP concentration of standard solution
Relation drawing curve, the test limit for obtaining BaP reaches 10-15 mol·L-1The order of magnitude, density of photocurrent is with BaP concentration
Change curve is as shown in Figure 2.After the completion of each photoelectric current is determined, used working electrode is individually placed in ethanol and acetone
Alternately clean, be repeated 3 times to remove the microsphere of absorption, electrode is regenerated and is updated.
Embodiment 3
The molL of blank solution 0.1 is determined respectively-1PBS（Containing 0.1 molL-1AA, PH=7.4）With containing a certain dense
Spend BaP 0.1 molL-1PBS（Containing 0.1 molL-1AA, PH=7.4）Standard liquid and containing with times concentration BaP do
Disturb material（Such as benzene, naphthalene, pyrene）0.1 molL-1PBS（Containing 0.1 molL-1AA, PH=7.4）Solution as electrolyte,
Using three-electrode system as described in example 2 above, the corresponding photoelectric current of different electrolytes is measured, passes through the working face of working electrode
Product calculating obtains the respective density of photocurrent of different electrolytes.As a result show, in the above-mentioned electricity containing BaP and containing interfering material
In solution liquid density of photocurrent has different degrees of increase compared with blank electrolysis liquid, but the density of photocurrent of the detection for BaP
Influence is respectively less than 22%, and this shows according to being prepared described in embodiment 1 based on BaP molecular imprinting functionalization CdS/3DOM in situ
TiO2/ BDD electrodes have good selective analysis ability.
The above-mentioned description to embodiment is understood that for the ease of those skilled in the art and using this
Invention.Person skilled in the art obviously can easily make various modifications to these embodiments, and illustrating herein
General Principle be applied in other embodiment without passing through performing creative labour.Therefore, the invention is not restricted to reality here
Example is applied, those skilled in the art are according to the announcement of the present invention, and the improvement made for the present invention and modification all should be in the present invention
Protection domain within.
Claims (3)
1. a kind of molecular imprinting functionalization CdS/3DOM TiO in situ2The photoelectric analysis method of/BDD electrode pair BaPs, its feature
It is to comprise the following steps that：
（1）The pretreatment of BDD electrodes：Using pending BDD electrodes as working electrode, platinum electrode is auxiliary electrode, and saturation is sweet
Mercury electrode is reference electrode, is placed in 1 ~ 2molL-1 H2SO4In solution, 20 ~ 30min is cleaned using -3 ~ 3V multisteps potentiometry,
Then take out BDD electrodes, and cleaned with deionized water, be subsequently placed at water-bath in chloroazotic acid and boil 10 ~ 20min, finally by electrode according to
It is secondary to be cleaned by ultrasonic in deionized water, acetone, deionized water, after drying naturally, obtain the BDD electrodes of cleaning；
（2）3DOM TiO on BDD electrodes2Preparation：
(2.1) pretreated BDD electrodes are placed on by the poly- of 0.1 ~ 0.5%wt using hard template method combination sol-gel process vertically
In styrene PS microsphere suspension liquids, 40 ~ 60 DEG C of drying in baking oven are placed in, PS microballoons is uniformly assembled in BDD electrode surfaces；
(2.2) TiO is prepared2Dense HCl, i.e., be added in butyl titanate by precursor solution, stirring, while adding ethanol can obtain
TiO2Precursor solution, wherein：Dense HCl, butyl titanate and ethanol volume ratio are 1:2.5:6；
(2.3) the above-mentioned BDD electrodes for being assembled with PS microballoons are slowly immersed in TiO2In precursor solution, stand after 20 ~ 50s, with 1 ~
3mm/s speed is slowly withdrawn BDD electrodes, is then placed within baking oven, is dried 1 ~ 2 hour under the conditions of 50 ~ 80 DEG C；
(2.4) electrode for obtaining step (2.3), which is put in tube furnace, carries out two step calcination processings, and calcining heat is respectively 300
DEG C and 400 DEG C, often walk the calcining at constant temperature time be 1 ~ 3h, heating rate be 2 ~ 5 DEG C/min, obtain 3DOM TiO2/ BDD electrodes；
（3）The assembling of BaP original positions molecular imprinting functionalization CdS nano-particles：Using SILAR method by step
（2）The 3DOM TiO of middle preparation2/ BDD electrodes immerse 0.02 ~ 0.06 molL successively-1Containing 0.1 ~ 0.5mmolL-1BaP Cd
(NO3)2Solution, 0.02 ~ 0.06 molL-1Containing 0.1 ~ 0.5mmolL-1BaP Na2S solution, deionized water 1, deionization
In water 2, a cycle period, 3DOM TiO are designated as2Dip time of/BDD the electrodes in each solution is 10 ~ 30s；Circulation leaching
After 10 ~ 20 cycles of stain, electrode is taken out, is placed in tube furnace, in N2400 ~ 500 DEG C of 2 ~ 3h of calcining, heating are carried out under atmosphere
Speed is 2 ~ 5 DEG C/min, obtains CdS/3DOM TiO after Temperature fall2/ BDD electrodes；
（4）BaP photoelectric analysis：Prepare 0.1 ~ 0.2 molL of BaP containing various concentrations a series of-1PBS standard liquids are distinguished
It is used as electrolyte, 0.1 ~ 0.2 molL-1PBS standard liquids are containing 0.1 ~ 0.2 molL-1The solution of AA, pH=7.0 ~ 8.0,
With prepared CdS/3DOM TiO2/ BDD electrodes set up three-electrode system as working electrode, put the electrodes into electrolyte
In, stood after 5 ~ 10 min of stirring；Using chronoamperometry, under visible light illumination, apply 0 ~ 0.3V biass, determine photoelectricity
Stream；Density of photocurrent is calculated by the work area of working electrode, and according to density of photocurrent and the line of concentration of standard solution
Sexual intercourse drawing curve；Working electrode is taken out after the completion of determining every time, the alternate agitation cleaning 2 ~ 5 in ethanol and acetone
It is secondary, the microsphere of absorption is removed, electrode surface is regenerated and is updated；
(5) CdS/3DOM TiO2The selective light electroanalysis of/BDD electrodes：Prepare respectively containing disturbance material 0.1 ~
0.2 mol·L-1PBS solution, 0.1 ~ 0.2 molL-1PBS solution is containing 0.1 ~ 0.2 molL-1AA, pH=7.0 ~ 8.0
Solution, and respectively as electrolyte, with prepared CdS/3DOM TiO2/ BDD electrodes are as working electrode, using step
（4）Methods described, determines photoelectric current of the electrode in disturbance thing solution, calculates density of photocurrent, comparison electrode exists respectively
Density of photocurrent in the BaP standard liquids of same concentrations, calculates jamming rate of each interfering material for BaP, determines every time
After the completion of working electrode is taken out, in ethanol and acetone alternate agitation clean 2 ~ 5 times, remove absorption interfering material, make electricity
Pole surface is regenerated and updated.
2. molecular imprinting functionalization CdS/3DOM TiO in situ according to claim 12The photoelectricity of/BDD electrode pair BaPs
Analysis method, it is characterised in that the solution containing interfering material is by 5.0 × 10-12 mol·L-1BaP points of test substance
Interfering material not with the BaP of same concentrations is mixed, the selection performance of inspecting electrode.
3. molecular imprinting functionalization CdS/3DOM TiO in situ according to claim 22The photoelectricity of/BDD electrode pair BaPs
Analysis method, it is characterised in that the interfering material is coexists with BaP in environment, and the similar multiring aromatic hydrocarbon pollution of structure
Thing benzene, naphthalene, pyrene.
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| 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 |
| CN107064263B (en) * | 2017-05-09 | 2019-04-16 | 同济大学 | Aptamer photoelectric sensor and preparation method thereof for detecting Atrazine |
| 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 |
| 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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| Functionalized Graphite Platelets and Lead Sulfide Quantum Dots Enhance Solar Conversion Capability of a Titanium Dioxide/Cadmium Sulfide Assembly;P. Naresh Kumar et. al;《Journal of Physical Chemistry C》;20140728;第118卷(第33期);全文 * |
| Sensitive Detection of Polycyclic Aromatic Hydrocarbons Using CdTe Quantum Dot-Modified TiO2 Nanotube Array through Fluorescence Resonance Energy Transfer;Lixia Yang, Beibei Chen et.al;《Environmental Science & Technology》;20100917;第44卷(第20期);全文 * |
| Spectral sensitization of a TiO2 semiconductor electrode by CdS microcrystals and its photoelectrochemical properties;S. Kohtani, A. Kudo, T. Sakata;《Chemical Physics Letters》;20020110;第206卷(第1-4期);全文 * |
| 二氧化钛基复合材料的制备及电化学与光电性能研究;曹慧敏;《中国博士学位论文全文数据库 工程科技I辑》;20120815(第8期);第2、3章 * |
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