CN109613098A - The preparation method and application of automatically cleaning electrochemical sensor under a kind of visible light - Google Patents
The preparation method and application of automatically cleaning electrochemical sensor under a kind of visible light Download PDFInfo
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- CN109613098A CN109613098A CN201810776679.1A CN201810776679A CN109613098A CN 109613098 A CN109613098 A CN 109613098A CN 201810776679 A CN201810776679 A CN 201810776679A CN 109613098 A CN109613098 A CN 109613098A
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Abstract
The invention discloses a kind of electrochemical sensor with self-cleaning ability, the TiO being sensitized including electrode cores and (4- carboxyl phenyl) porphyrin metal complex of meso- tetra-2Combined oxidation graphene modified material, and the composite modified material attachment is on the chip surface.The preparation method of the sensor is simple, it is time saving, it is at low cost, it is environmental-friendly, the especially residual of the sensor polymer for being attached to electrode chip surface after detection having and detectable substance can be oxidized under visible light conditions, reach the regeneration and self-cleaning effect of electrochemical sensor under visible light.Regenerated electrochemical sensing platform not only reduces the complicated procedures of electrode polishing modification under visible light, has also saved the cost of decorative material, and the de-sludging regeneration of electrode extends the service life of electrode.Easy to operate for the detection of environmental contaminants nitrophenol, selectively good, high sensitivity, detection limit are low.
Description
Technical field
The present invention relates to the preparation technical fields of electrochemical sensor, and in particular to automatically cleaning electrochemistry under a kind of visible light
The preparation method and application of sensor, the sensor are the electrochemical sensor for measuring nitrophenol, are had under visible light
Reach self-cleaning ability.
Background technique
Electrochemical sensing technology the fields such as biochemical, medical treatment, food product environment monitoring show higher detectability and
Effect, electrochemical analysis method is with inexpensive, analysis speed is fast, detection performance is good, sample consumption is few, high sensitivity, selection
The advantages that property is good, operation is convenient, the preprocessing process of no complexity.It is for biological sample, environmental monitoring and food security aspect
It can reach quantitative detection and analysis.However, chemical reaction occurs in electrode and solution surface for electrochemical method,
In electrochemical reaction process, due to the aggregation and deposition of analyte and product, often to the surface state of electrochemical sensor
Changing makes electrode passivation or inactivation, to influence the sensitivity and selectivity of the electrode, how to solve electrode itself passivation
Problem is the hot spot of current electrochemical analysis research aspect.Nowadays common processing method has physical mechanical sanding and polishing, changes
Oxidation or reduction, electrochemical oxidation or reduction etc. are learned, but these methods more or less can all have an impact electrode itself, damage
The surface of bad electrochemical sensor but will cause the stability of electrochemical sensor poor, keep Electrochemical Detection result inconsistent.
Therefore, it under the premise of not changing electrochemical sensor surface and chemical property, is made a return journey using the method for mild easy green
Except the pollutant on electrochemical sensor surface reaches self-cleaning effect, it is of great significance for electrochemical analysis method.
TiO2As a kind of photochemical catalyst, light degradation can be carried out for pollutant under the conditions of not influencing surface texture,
Photohole and electronics pair can be generated under light illumination, and the extremely strong hydroxyl free of oxidisability can be generated in conjunction with the oxygen in air and water
Base (OH), and it to the no selectivity of the oxidation of substance, can degrade most organic pollutants, often be used as photocatalysis
The self-cleaning material of initiation.However the band gap of titanium dioxide is larger, about 3.2eV, and the purple of 387nm can only be lower than by wavelength
Outer light excitation, which greatly limits TiO2Use, select suitable photosensitizer, the forbidden bandwidth of titanium dioxide made to narrow,
Light degradation effect can be generated under visible light conditions, all had for the reduction of its photodegradative use scope and energy consumption
Important meaning.
Meso- tetra- (4- carboxyl phenyl) porphyrin metal complex is a kind of relatively conventional photosensitizer, metalloporphyrin load
On the titanium dioxide, metalloporphyrin absorbs visible light, becomes the metalloporphyrin of excitation state, and excitation metalloporphyrin arrives electron transmission
TiO2On conduction band, the oxygen in conduction band in electronics and solution generates O2 -, then through series reaction OH is generated, finally make TiO2Energy
There is light degradation effect under visible light conditions, to form Visible Light Induced Photocatalytic material.
TiO2As a kind of semiconductor, conductivity is lower, as common photochemical catalyst, all has poor electrochemistry
Activity is not suitable for as directly as electrochemical sensor material.Graphene is as a kind of novel two-dimentional carbon nanomaterial, tool
There is excellent electric conductivity, electron mobility is higher compared with carbon nanotube, for this purpose, it is usually that graphene and photochemical catalyst is compound, it mentions
The electron transmission efficiency of high sensing capabilities and photocatalysis efficiency, graphene oxide can reduce the compound of photo-generated carrier, thus
Improve the disposal efficiency.
P-nitrophenol (4-nitrophenol, 4-NP) is a kind of common high toxicity environmental contaminants, is applied extensively
In insecticide, dyestuff, drug production serious environmental contaminants, be normally present in industrial wastewater and soil, and when it can be long
Between exist in the environment, have high toxicity and carcinogenic possibility, 4- nitrophenol by Environmental Protection Agency USA be considered phenol and
Have in its derivative pollutant compared with one of high toxicity environmental contaminants.The common method of detection to 4-NP has gas-chromatography
Method, liquid chromatography, fluorescence spectrophotometry, ultraviolet spectroscopy etc., however, to be commonly present some problems for example many and diverse for these methods
Pretreatment process, interminable analysis time, analysis instrument valuableness etc..And electrochemical analysis method is simple to operate, quick spirit
It is quick, be easy to minimize, the advantages that cost is relatively low, is commonly used for detection for environmental contaminants.
By the TiO of graphene oxide and the sensitization of (4- carboxyl phenyl) porphyrin metal complex of meso- tetra-2It is compound, it is expected to
Maintain electrode electro Chemical sensing capabilities while, under visible light conditions, with electrode later carry out can with automatically cleaning and activation,
It can be made to regenerate and there is detection activity again, and its is easy to operate, environmentally protective, low energy consumption, can be used for environment dirt
The detection of object nitrophenol is contaminated, it is a worth further investigated that the self-cleaning ability of the sensor, which has potential application,
Project.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, it is an object of the invention to: providing one kind can be easy, low
The electrochemical sensor of cost, high sensitivity measuring nitrophenol has self-cleaning ability, and certainly under visible light conditions
Cleaning effect does not influence its chemical property.
Electrochemical sensor of the present invention includes electrode cores and dispersion liquid, the dispersion liquid be graphene oxide with
The TiO of (4- carboxyl phenyl) porphyrin metal complex of meso- tetra- sensitization2Nano material is combined, the dispersion liquid that will be prepared
Drop coating is in obtaining electrochemical sensor in electrode cores.Electrochemical sensor of the invention can be in the electrochemistry for meeting p-nitrophenol
While detection, under visible light, reaches a self-cleaning effect, regeneration electrode and extension electrode life, solve electrode
Problem of passivation, the time waste and consumptive material for reducing electrochemical electrode treatment process use.
Specific technical solution is as follows:
A kind of electrochemical sensor, the drop coating layer including electrode cores He its surface, the drop coating layer are applied to by dispersant liquid drop
Electrode wicking surface is formed, and the dispersion liquid is that graphene oxide and (4- carboxyl phenyl) porphyrin metal complex of meso- tetra- are sensitized
TiO2Nano material is combined.During preparing dispersion liquid, matched using meso- tetra- (4- carboxyl phenyl) porphyrin metal
Object is closed as photosensitizer sensitization TiO2Material, then with graphene oxide is compound obtains dispersion liquid, dispersant liquid drop is applied to electrode
Electrochemical sensor is obtained on core, which irradiates under visible light, that is, can reach clearing electrode surface contaminant
Self-cleaning effect.
The dispersion liquid the preparation method is as follows: by mass ratio (0.5-2): the graphene oxide of 1 (preferably 1:1) with
The TiO of (4- carboxyl phenyl) porphyrin metal complex of meso- tetra- sensitization2Material is put into container, then solvent is added into container
A, ultrasound 2-4h, obtains dispersion liquid in ultrasonic instrument.
The solvent A is one or more of n,N-Dimethylformamide, dimethyl sulfoxide and N-Methyl pyrrolidone,
Solvent A dosage are as follows: every 1mg graphene oxide uses 2-25mL solvent A；
Preferably, solvent A dosage are as follows: every 1mg graphene oxide uses 5-15mL solvent A.
The TiO of tetra- (4- carboxyl phenyl) porphyrin metal complex of the meso- sensitization2The preparation method of material is: will
Meso- tetra- (4- carboxyl phenyl) porphyrin metal complex is dissolved in solvent B, and TiO is added thereto2(preferably through 120 DEG C,
TiO after 2h drying process2Powder), 2-6h is stirred at room temperature, and decompression rotary evaporation falls solvent B, collects and grind institute
Solid is obtained, it is dry (the dry 30min preferably at 80 DEG C).
Preferably, the mass ratio of meso- tetra- (4- carboxyl phenyl) porphyrin metal complex and titanium dioxide additional amount
For 5-10mg:1g, most preferably 7.7mg:1g.
Preferably, the solvent B is chloroform.
Preferably, the TiO2For titanium dioxide P25.
Preferably, the graphene oxide is single-layer graphene oxide, and lamella diameter is 1-5 μm, thickness about 0.8-
1.2nm。
Meso- tetra- (4- carboxyl phenyl) porphyrin metal complex are as follows: meso- tetra- (4- carboxyl phenyl) porphyrin copper,
Meso- tetra- (4- carboxyl phenyl) porphyrin iron chloride, meso- tetra- (4- carboxyl phenyl) porphyrin palladium, meso- tetra- (4- carboxyl phenyl) porphin
At least one of quinoline zinc, (4- carboxyl phenyl) the porphyrin platinum of meso- tetra- and meso- tetra- (4- carboxyl phenyl) Cobalt Porphyrin.
It is furthermore preferred that (4- carboxyl phenyl) porphyrin metal complex of meso- tetra- is meso- tetra- (4- carboxyl phenyl) porphyrin
Copper.
A kind of preparation method of above-mentioned electrochemical sensor, includes the following steps:
(1) TiO for being sensitized (4- carboxyl phenyl) porphyrin metal complex of meso- tetra-2Combined oxidation graphene dispersing solution
Drop coating is placed in 40-80 DEG C of vacuum oven and dries in polished and cleaning, dried electrode surface；
(2) electrode that step (1) obtains successively is cleaned with NaAc_HAc buffer solution and secondary distilled water and obtains electricity
Chemical sensor.
The electrode is glass-carbon electrode, gold electrode or copper electrode, preferably glass-carbon electrode.
The TiO of (4- carboxyl phenyl) porphyrin metal complex of meso- tetra- sensitization2It is produced between material and graphene oxide layer
Raw π-π is acted on and is more advantageous to electron transmission, enhances electronics conduction velocity, enhances detection effect；It also can be reduced photoproduction load simultaneously
Compound, the enhancing TiO of stream2Light degradation effect, play self-cleaning ability.
Above-mentioned electrochemical sensor is being applied to nitrophenol (including p-nitrophenol, o-nitrophenol and/or nitre
Base phenol, especially p-nitrophenol) detection when effect it is preferable, and self-cleaning effect can be played under visible light conditions, had wide
Wealthy application prospect.
Advantages of the present invention:
The TiO of (4- carboxyl phenyl) porphyrin metal complex of meso- tetra- sensitization is prepared by simple preparation method2It is compound
Graphene oxide dispersion modifies electrode surface with drop-coating, prepares meso- tetra- (4- carboxyl phenyl) porphyrin metal
The TiO of complex sensitization2Combined oxidation Graphene electrodes have preferable detection effect, the range of linearity to p-nitrophenol are as follows:
0.5 μm of ol/L-100 μm of ol/L, detection limit are as follows: 0.16 μm of ol/L.
Emphasis of the invention is the building of the self-cleaning effect to the electrochemical sensing platform after detection, and automatically cleaning
Effect constructs relatively simple green, using graphene oxide, enhances electron transfer rate and is TiO2Biggish attachment position is provided
Point, so that preferable self-cleaning ability can be had while enhancing electronics conductive process by playing, only placement is under visible light
It can reach self-cleaning effect, can repeatedly recycle for the detection to determinand.
The method of the present invention is easy to operate, time saving, at low cost, detection sensitivity is higher, and it is expensive to solve existing determination techniques
Cumbersome, the complicated problem time-consuming, detection sensitivity is not high of electrochemical sensor preparation, while to the detection effect of p-nitrophenol
Preferably, there is preferable self-cleaning effect, electrode life is obviously prolonged after automatically cleaning, has wide application prospect.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) figure of electrochemical sensor A1 in embodiment 1.
Fig. 2 is Cu (II) TCPP/TiO in embodiment 1 in electrochemical sensor in A12Ultraviolet-visible absorption spectroscopy
Figure.
Fig. 3 is X-ray diffractogram (XRD) figure of electrochemical sensor A1 in embodiment 1.
Fig. 4 is when being detected using the electrochemical sensor A1 of embodiment 1, and different scanning speed is to p-nitrophenol (4-NP)
The influence of redox peaks current-responsive.
Fig. 5 is enrichment time (Fig. 5 A), accumulating potential (Fig. 5 B) when being detected using the electrochemical sensor A1 of embodiment 1
The influence that paracetamol oxidation peak current is responded with pH value (Fig. 5 C).
Fig. 6 a is when being detected using the electrochemical sensor A1 of embodiment 1, and oxidation peak current response is dense with p-nitrophenol
The linear relationship chart of degree (a-k respectively corresponds concentration: 0,0.5,1,2,4,8,10,20,60,80,100 μm of ol/L)；Fig. 6 b is benefit
When being detected with comparative example D1, oxidation peak current response and the linear relationship chart of p-nitrophenol concentration (a-g respectively corresponds concentration:
0、1、2、4、8、10、20μmol/L)。
Fig. 7 A is Cu (II) TCPP/TiO after detecting A1 using electrochemical sensor in embodiment 12/ GO electrode surface exists
Curent change figure under visible light under automatically cleaning, Fig. 7 B are D1 electrode table after being detected using electrochemical sensor D1 in comparative example 1
Curent change figure under the visible light of face under automatically cleaning, Fig. 7 C are A1 and D1 current-responsive variation diagram in an automatically cleaning period.
Specific embodiment
The present invention is described in further detail in the following with reference to the drawings and specific embodiments.
In the following Examples and Comparative Examples, meso- tetra- (4- carboxyl phenyl) porphyrin metal complex is purchased from Beijing hundred
Ling Wei Science and Technology Ltd.；Graphene oxide (GO) is purchased from Nanjing Ji Cang nanosecond science and technology Co., Ltd JCGO-99-1-2, is single layer
Graphene oxide, 1-5 μm of lamella diameter, thickness about 0.8-1.2nm, spectroscopic pure, purity > 99%；Electrode used therein is high purchased from Wuhan
Shi Ruilian Science and Technology Ltd., the diameter of electrode cores are 3mm；Nitric acid solution is the concentrated nitric acid for using 65-68wt% and water with body
Product is formulated than 1:1；Dehydrated alcohol is purchased from Sinopharm Chemical Reagent Co., Ltd., analyzes pure；TiO used2Moral is created to win
The nano-titanium dioxide P25 of Gu Sai company, average grain diameter 21nm, anatase/rutile mass ratio are about 80/20, BET method ratio
Surface area is about 50 ± 15m2/g。
Embodiment 1:
A kind of preparation method of electrochemical sensor under visible light with self-cleaning ability, in turn includes the following steps:
(1) 7.7mg meso- tetra- (4- carboxyl phenyl) porphyrin copper (Cu (II) TCPP) is weighed with electronic balance, is put into 50ml
In single neck flask, 20mL solvent chloroform is added thereto dissolves Cu (II) TCPP, then adds and does through 120 DEG C, 2h
Dry treated TiO21g, in stirring 4h under room temperature, decompression rotary evaporation falls chloroform, collects and grinds gained admittedly
Body, the TiO of Cu (II) TCPP sensitization is made in dry 30min under the conditions of 80 DEG C2, it is denoted as Cu (II) TCPP/TiO2, it is ultraviolet can
See that absorption figure is as shown in Figure 2；
(2) graphene oxide (GO) of 1.0mg and Cu (II) TCPP/TiO of 1.0mg are weighed respectively2It is added to 10mL and burns
It in cup, then takes the DMF (n,N-Dimethylformamide) of 10mL in beaker with pipette, is put into ultrasound 3h in ultrasonoscope, obtains
To Cu (II) TCPP/TiO2/ GO dispersion liquid；
(3) it takes the neutral alumina (0.05 μm) of 20mg in being soaked on polishing cloth with water, glass-carbon electrode (Φ=3mm) is existed
Mirror surface is polished on polishing cloth；
(4) successively it is cleaned by ultrasonic above-mentioned glass-carbon electrode 2min respectively with nitric acid solution, dehydrated alcohol, secondary distilled water again,
It is cleaned with secondary distilled water after cleaning, is finally dried under infrared lamp every time；
(5) Cu (II) TCPP/TiO for taking 5 μ L steps (2) to prepare2/ GO dispersant liquid drop is applied to the glass-carbon electrode table of drying
Face is dried in 45 DEG C of vacuum ovens；
(6) electrode that step (5) obtains successively is used into 0.2molL-1The NaAc_HAc buffer solution of pH=5.5, two
Secondary distilled water is cleaned, and it is A1 that electrochemical sensor, which is prepared, and SEM and XRD diagram are as shown in figures 1 and 3.
Embodiment 2:
A kind of preparation method of electrochemical sensor under visible light with self-cleaning ability, in turn includes the following steps:
(1) 7.7mg meso- tetra- (4- carboxyl phenyl) porphyrin iron chloride (Fe (III) TCPP) is weighed with electronic balance, put
Enter in the mono- neck flask of 50ml, 20mL solvent chloroform is added thereto dissolves Fe (III) TCPP, then adds through 120
DEG C, 2h be dried after TiO21g, in stirring 4h under room temperature, decompression rotary evaporation falls solvent chloroform, collects simultaneously
Obtained solid is ground, the TiO of Fe (III) TCPP sensitization is made in dry 30min under the conditions of 80 DEG C2, it is denoted as Fe (III) TCPP/
TiO2；
(2) graphene oxide (GO) of 1.0mg and Fe (III) TCPP/TiO of 1.0mg are weighed respectively2It is added to 10mL and burns
It in cup, then takes the DMF of 10mL in beaker with pipette, is put into ultrasound 3h in ultrasonoscope, obtains Fe (III) TCPP/TiO2/
GO dispersion liquid；
(3) it takes the neutral alumina (0.05 μm) of 20mg in being soaked on polishing cloth with water, glass-carbon electrode (Φ=3mm) is existed
Mirror surface is polished on polishing cloth；
(4) successively it is cleaned by ultrasonic above-mentioned glass-carbon electrode 2min respectively with nitric acid solution, dehydrated alcohol, secondary distilled water again,
It is cleaned with secondary distilled water after cleaning, is finally dried under infrared lamp every time；
(5) Fe (III) TCPP/TiO for taking 5 μ L steps (2) to prepare2/ GO dispersant liquid drop is applied to the glass-carbon electrode table of drying
Face is dried in 45 DEG C of vacuum ovens；
(6) electrode that step (5) obtains successively is used into 0.2molL-1The NaAc_HAc buffer solution of pH=5.5, two
Secondary distilled water is cleaned, and it is A2 that electrochemical sensor, which is prepared,.
Embodiment 3:
A kind of preparation method of electrochemical sensor under visible light with self-cleaning ability, in turn includes the following steps:
(1) 7.7mg meso- tetra- (4- carboxyl phenyl) porphyrin palladium (Pd (II) TCPP) is weighed with electronic balance, is put into 50ml
In single neck flask, 20mL solvent chloroform is added thereto dissolves Pd (II) TCPP, then adds and does through 120 DEG C, 2h
Dry treated TiO21g, in stirring 4h under room temperature, decompression rotary evaporation falls solvent chloroform, collects and grind institute
Solid is obtained, the TiO of Pd (II) TCPP sensitization is made in dry 30min under the conditions of 80 DEG C2, it is denoted as Pd (II) TCPP/TiO2；
(2) graphene oxide (GO) of 1.0mg and Pd (II) TCPP/TiO of 1.0mg are weighed respectively2It is added to 10mL and burns
It in cup, then takes the DMF of 10mL in beaker with pipette, is put into ultrasound 3h in ultrasonoscope, obtains Pd (II) TCPP/TiO2/
GO dispersion liquid；
(3) it takes the neutral alumina (0.05 μm) of 20mg in being soaked on polishing cloth with water, glass-carbon electrode (Φ=3mm) is existed
Mirror surface is polished on polishing cloth；
(4) successively it is cleaned by ultrasonic above-mentioned glass-carbon electrode 2min respectively with nitric acid solution, dehydrated alcohol, secondary distilled water again,
It is cleaned with secondary distilled water after cleaning, is finally dried under infrared lamp every time；
(5) Pd (II) TCPP/TiO for taking 5 μ L steps (2) to prepare2/ GO dispersant liquid drop is applied to the glass-carbon electrode table of drying
Face is dried in 45 DEG C of vacuum ovens；
(6) electrode that step (5) obtains successively is used into 0.2molL-1The NaAc_HAc buffer solution of pH=5.5, two
Secondary distilled water is cleaned, and it is A3 that electrochemical sensor, which is prepared,.
Embodiment 4:
A kind of preparation method of electrochemical sensor under visible light with self-cleaning ability, in turn includes the following steps:
(1) 7.7mg meso- tetra- (4- carboxyl phenyl) porphyrin platinum (Pt (II) TCPP) is weighed with electronic balance, is put into 50ml
In single neck flask, 20mL solvent chloroform is added thereto dissolves Pt (II) TCPP, then adds and does through 120 DEG C, 2h
Dry treated TiO21g, in stirring 4h under room temperature, decompression rotary evaporation falls solvent chloroform, collects and grind institute
Solid is obtained, the TiO of Pt (II) TCPP sensitization is made in dry 30min under the conditions of 80 DEG C2, remember Pt (II) TCPP/TiO2；
(2) graphene oxide (GO) of 1.0mg and Pt (II) TCPP/TiO of 1.0mg are weighed respectively2It is added to 10mL and burns
It in cup, then takes the DMF of 10mL in beaker with pipette, is put into ultrasound 3h in ultrasonoscope, obtains Pt (II) TCPP/TiO2/
GO dispersion liquid；
(3) it takes the neutral alumina (0.05 μm) of 20mg in being soaked on polishing cloth with water, glass-carbon electrode (Φ=3mm) is existed
Mirror surface is polished on polishing cloth；
(4) successively it is cleaned by ultrasonic above-mentioned glass-carbon electrode 2min respectively with nitric acid solution, dehydrated alcohol, secondary distilled water again,
It is cleaned with secondary distilled water after cleaning, is finally dried under infrared lamp every time；
(5) Pt (II) TCPP/TiO for taking 5 μ L steps (2) to prepare2/ GO dispersant liquid drop is applied to the glass-carbon electrode table of drying
Face is dried in 45 DEG C of vacuum ovens；
(6) by electrode that step (5) obtains successively with using 0.2molL-1The NaAc_HAc buffer solution of pH=5.5,
Secondary distilled water is cleaned, and it is A4 that electrochemical sensor, which is prepared,.
Embodiment 5:
A kind of preparation method of electrochemical sensor under visible light with self-cleaning ability, in turn includes the following steps:
(1) 7.7mg meso- tetra- (4- carboxyl phenyl) zinc porphyrin (Zn (II) TCPP) is weighed with electronic balance, is put into 50ml
In single neck flask, 20mL solvent chloroform is added thereto dissolves Zn (II) TCPP, then adds and does through 120 DEG C, 2h
Dry treated TiO21g, in stirring 4h under room temperature, decompression rotary evaporation falls solvent chloroform, collects and grind institute
Solid is obtained, the TiO of Zn (II) TCPP sensitization is made in dry 30min under the conditions of 80 DEG C2, remember Zn (II) TCPP/TiO2；
(2) graphene oxide (GO) of 1.0mg and Zn (II) TCPP/TiO of 1.0mg are weighed respectively2It is added to 10mL and burns
It in cup, then takes the DMF of 10mL in beaker with pipette, is put into ultrasound 3h in ultrasonoscope, obtains Zn (II) TCPP/TiO2/
GO dispersion liquid；
(3) it takes the neutral alumina (0.05 μm) of 20mg in being soaked on polishing cloth with water, glass-carbon electrode (Φ=3mm) is existed
Mirror surface is polished on polishing cloth；
(4) successively it is cleaned by ultrasonic above-mentioned glass-carbon electrode 2min respectively with nitric acid solution, dehydrated alcohol, secondary distilled water again,
It is cleaned with secondary distilled water after cleaning, is finally dried under infrared lamp every time；
(5) 5 μ L steps (2) is taken to prepare Zn (II) TCPP/TiO2The dispersant liquid drop of/GO is applied to the glass-carbon electrode table of drying
Face is dried in 45 DEG C of vacuum ovens；
(6) electrode that step (5) obtains successively is used into 0.2molL-1The NaAc_HAc buffer solution of pH=5.5, two
Secondary distilled water is cleaned, and it is A5 that electrochemical sensor, which is prepared,.
Embodiment 6:
A kind of preparation method of electrochemical sensor under visible light with self-cleaning ability, in turn includes the following steps:
(1) 7.7mg meso- tetra- (4- carboxyl phenyl) porphyrin copper cobalt (Co (II) TCPP) is weighed with electronic balance, be put into
In the mono- neck flask of 50ml, thereto be added 20mL solvent chloroform make Co (II) TCPP dissolve, then add in 120 DEG C,
TiO after 2h drying process21g, in stirring 4h under room temperature, decompression rotation falls dry solvent chloroform, collects and grind
Obtained solid is ground, the TiO of Co (II) TCPP sensitization is made in dry 30min under the conditions of 80 DEG C2, remember Co (II) TCPP/TiO2；
(2) graphene oxide (GO) for weighing 1.0mg respectively weighs Co (II) TCPP/TiO of 1.0mg2It is added to 10mL
It in beaker, then takes the DMF of 10mL in beaker with pipette, is put into ultrasound 3h in ultrasonoscope, obtains Co (II) TCPP/
TiO2/ GO dispersion liquid；
(3) it takes the neutral alumina (0.05 μm) of 20mg in being soaked on polishing cloth with water, glass-carbon electrode (Φ=3mm) is existed
Mirror surface is polished on polishing cloth；
(4) successively it is cleaned by ultrasonic above-mentioned glass-carbon electrode 2min respectively with nitric acid solution, dehydrated alcohol, secondary distilled water again,
It is cleaned with secondary distilled water after cleaning, is finally dried under infrared lamp every time；
(5) 5 μ L steps (2) is taken to prepare Co (II) TCPP/TiO2The dispersant liquid drop of/GO is applied to the glass-carbon electrode table of drying
Face is dried in 45 DEG C of vacuum ovens；
(6) by electrode that step (5) obtains successively with using 0.2molL-1The NaAc_HAc buffer solution of pH=5.5,
Secondary distilled water is cleaned, and it is A6 that electrochemical sensor, which is prepared,.
Comparative example 1:
A kind of preparation method of graphene oxide electrochemical sensor, in turn includes the following steps:
(1) weigh 1.0mg graphene oxide (GO) be added into 10mL beaker, then with pipette take the DMF of 10mL in
In beaker, it is put into ultrasound 3h in ultrasonoscope, obtains GO dispersion liquid；
(2) it takes the neutral alumina (0.05 μm) of 20mg in being soaked on polishing cloth with water, glass-carbon electrode (Φ=3mm) is existed
Mirror surface is polished on polishing cloth；
(4) successively it is cleaned by ultrasonic above-mentioned glass-carbon electrode 2min respectively with nitric acid solution, dehydrated alcohol, secondary distilled water again,
It is cleaned with secondary distilled water after cleaning, is finally dried under infrared lamp every time；
(5) dispersant liquid drop for taking 5 μ L steps (1) to prepare GO is applied to the glassy carbon electrode surface of drying, is dried in vacuo at 45 DEG C
It is dried in case；
(6) the electrode 0.2molL for obtaining step (5)-1The hac buffer and second distillation of pH=5.5 is washed
Only, it is D1 that electrochemical sensor, which is prepared,.
Experimental example 1
It is carried out using the electrochemical sensor A1 prepared in embodiment 1 by sample of the square wave voltammetry to p-nitrophenol
Analysis detection, meanwhile, the photodegradative automatically cleaning signal of modified electrode is detected.
Prepare p-nitrophenol (4-NP) solution:
It is dissolved in 2mL water with electronic balance weighing p-nitrophenol (4-NP), prepares the p-nitrophenol of 0.001mol/L
Solution needs to be diluted to required concentration step by step according to experiment.
The measurement of p-nitrophenol (4-NP):
It using electrochemical sensor A1 as working electrode, saturated calomel electrode is reference electrode, platinum filament using square wave voltammetry
Electrode is that electrode is investigated different scanning speed, enrichment time, accumulating potential and pH value and rung to p-nitrophenol (4-NP) electric current
The influence answered.
When scanning speed is 10,40,70,100,130,160,200mV/s, 20 μm of ol/L p-nitrophenols (4-NP)
Current-responsive is respectively such as Fig. 4, it is known that its oxidation is a process by absorption and control.
When enrichment time is 10s, 30s, 50s, 70s, 90s, 120s, 150s, 180s, 10 μm of ol/L p-nitrophenols
The current-responsive of (4-NP) such as Fig. 5 A, it is known that best enrichment time is 70s.
When accumulating potential is respectively -0.6V, -0.4V, -0.2V, 0V, 0.2V, 0.4V, 0.6V, 10 μm of ol/L p-nitrophenyls
The current-responsive of phenol (4-NP) such as Fig. 5 B, it is known that best accumulating potential is 0V.
Secure ph are as follows: 3.5,4.0,4.5,5.0,5.5,6.0,6.5 0.2mol/L hac buffer pipettes respectively
For 10mL in beaker, the p-nitrophenol (4-NP) prepared in advance is added into beaker makes p-nitrophenol concentration 50 in solution
μm ol/L investigates influence of the pH value to p-nitrophenol current-responsive in -1.0-0.8V range, as a result as shown in Figure 5 c respectively
(a-g), discovery optimal pH is 5.5.
Using electrochemical sensor A1 be working electrode, saturated calomel electrode is reference electrode, platinum electrode be to electrode,
Assay is carried out using p-nitrophenyl phenol solution of the square wave voltammetry to various concentration, investigates current-responsive (I) and to nitro
The relationship of phenol (4-NP) concentration (c) is as follows: Ip(see Fig. 6 a, it is molten that a-k respectively corresponds p-nitrophenol to=1.10992c+12.45
Liquid concentration: 0,0.5,1,2,4,8,10,20,60,80,100 μm of ol/L).The slope of working curve is calculated by working curve
And utilize following formula meter sensitivity:
Sensitivity=slope/electrode core area
The sensitivity being calculated are as follows: 5.632AM-1·cm-2。
Same method investigates current-responsive (I) and p-nitrophenol (4-NP) concentration (c) with electrochemical sensor D1
Relationship (respectively corresponds p-nitrophenol solution concentration see Fig. 6 b, a-g: 0,1,2,4,8,10,20 μm of ol/L), obtains the sensitive of D1
Degree is 32.48AM-1·cm-2。
The measuring method of detection limit are as follows: continuously measured in blank solution 10 times with electrochemical sensor, calculate its standard
Deviation is detection limit with concentration value on curve corresponding to 3 times of standard deviations.The result shows that the detection of electrochemical sensor A1
It is limited to 0.16 μm of ol/L.The sensor D1 for similarly detecting comparative example is limited to 0.66 μm of ol/L to p-nitrophenol (4-NP) detection.
That is the A1 sensor of embodiment 1 is lower compared with the detection limit of the D1 sensor of comparative example 1, and detection range is wider.
Using the irradiation of visible light, the residue detection object on the electrode under different illumination conditions is measured, is made
With the electric current of square wave voltammetry (SWV) detecting electrode in blank NaAc_HAc buffer solution (0.2mol/L, pH=5.5)
Response, with this come the self-cleaning effect that reflects on electrochemical sensor (i.e. electrode surface), electrochemistry self-cleaning effect
As shown in Figure 7.
Detection is divided into the progress of five steps:
1. electrochemical sensor carries out current-responsive value when detecting for the first time to 20 μm of ol/L p-nitrophenols；2. detecting
After electrochemical sensor afterwards is simply rinsed with Acetic acid-sodium acetate buffer, the electric current in NaAc_HAc buffer solution is rung
It should be worth, i.e. the current responsing signal value of the residue of electrode surface attachment；3. the ultrapure water drop of electrode surface drop coating after detection
Current-responsive value after distinguishing illumination 1h afterwards with flashlight simulated visible light, in NaAc_HAc buffer solution；4. above-mentioned light
Current-responsive value after the electrode after 1h again illumination 1h, in NaAc_HAc buffer solution；5. the electricity after above-mentioned illumination 2h
Current-responsive value when being detected again to 20 μm of ol/L p-nitrophenols after extremely.
Fig. 7 A be using embodiment 1 A1 sensor carry out above-mentioned detection as a result, according to peak position out from top to bottom according to
The secondary above detecting step of correspondence 3. -4. -2. -5.-current-responsive value 1., it can be seen that after detecting for the first time, remained on electrode
There is detectable substance, after respectively illumination 1h and 2h, electric current levels off to baseline, and electrochemical response signal levels off to 0, again with this electrode
20 μm of ol/L p-nitrophenyl phenol solutions are detected, compared with first time is detected, peak current proves electrode certainly without significant change
Body cleaning action is preferable.
Fig. 7 B be using comparative example 1 D1 sensor carry out above-mentioned detection as a result, according to peak position out from top to bottom according to
The secondary above detecting step of correspondence 3. -4. -2. -5.-current-responsive value 1., it can be seen that GO modified electrode D1 is in 20 μm of ol/L
After p-nitrophenol solution to be measured carries out first time detection, detectable substance is remained on electrode, after illumination 1h and 2h respectively, electrode
Surface current variation, but variation is big without electrochemical sensor A1, detects again in 20 μm of ol/L p-nitrophenols, peak current letter
It number tests more for the first time much lower, it was demonstrated that D1 electrode causes to be detected residue or polymer inactivation without self-cleaning ability.
Fig. 7 C be embodiment 1 electrochemical sensor A1 and comparative example 1 sensor D1 (GO) electrode one from
Clean peak point current variation diagram in Period Process, abscissa numerical value 1,2,3,4,5 be illustrated respectively in above-mentioned steps 1. -5. lower carry out
Detection.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
The present invention is completed under the support of state natural sciences fund (No.21561011).
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of electrochemical sensor, it is characterised in that: the sensor includes the drop coating layer of electrode and electrode surface, the drop coating
Layer is applied to electrode surface by dispersant liquid drop and is formed, during preparing dispersion liquid, using meso- tetra- (4- carboxyl phenyl) porphyrin
Metal complex as photosensitizer sensitization titanic oxide material, then with graphene oxide is compound obtains dispersion liquid.
2. electrochemical sensor according to claim 1, which is characterized in that the dispersion liquid the preparation method is as follows: will
The titanium dioxide titanium of graphene oxide and (4- carboxyl phenyl) porphyrin metal complex of meso- tetra- sensitization of mass ratio 0.5-2:1
Material is put into container, then solvent A is added into container, and ultrasound 2-4h, obtains dispersion liquid in ultrasonic instrument.
3. electrochemical sensor according to claim 2, which is characterized in that the solvent A be n,N-Dimethylformamide,
One or more of dimethyl sulfoxide and N-Methyl pyrrolidone.
4. electrochemical sensor according to claim 3, which is characterized in that meso- tetra- (4- carboxyl phenyl) porphyrin
The preparation method of the titanic oxide material of metal complex sensitization is: by meso- tetra- (4- carboxyl phenyl) porphyrin metal complex
It is dissolved in solvent B, titanium dioxide is added thereto, stir 2-6h at room temperature, then remove solvent B, collect and grind
Obtained solid is ground, it is dry.
5. electrochemical sensor according to claim 4, it is characterised in that: the titanium dioxide being added thereto is warp
120 DEG C, 2h be dried after titania powder, tetra- (4- carboxyl phenyl) porphyrin metal complex of meso- and dioxy
The mass ratio for changing titanium additional amount is 5-10mg:1g.
6. electrochemical sensor according to claim 5, it is characterised in that: the solvent B is chloroform, removes solvent
The method of B is decompression rotary evaporation.
7. electrochemical sensor according to claim 1, it is characterised in that: meso- tetra- (4- carboxyl phenyl) porphyrin
Metal complex is meso- tetra- (4- carboxyl phenyl) porphyrin copper, meso- tetra- (4- carboxyl phenyl) porphyrin iron chloride, meso- tetra-
(4- carboxyl phenyl) porphyrin palladium, meso- tetra- (4- carboxyl phenyl) zinc porphyrin, (4- carboxyl phenyl) the porphyrin platinum of meso- tetra- and meso-
At least one of four (4- carboxyl phenyl) Cobalt Porphyrins.
8. a kind of preparation method of electrochemical sensor described in claim 1, it is characterised in that include the following steps:
(1) dispersant liquid drop is applied to polished and cleaning, dried electrode surface, is placed in 40-80 DEG C of vacuum oven
Middle drying；
(2) electrode that step (1) obtains is cleaned and obtains electrochemical sensor.
9. preparation method according to claim 8, it is characterised in that the electrode is glass-carbon electrode, gold electrode and copper electrode
One of.
10. a kind of electrochemical sensor as claimed in claim 1 to 7 measurement p-nitrophenol, o-nitrophenol and/or
Application in metanitrophenol.
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