CN104697945B - Visible light catalytic nano plasma COD sensors and its detection method - Google Patents
Visible light catalytic nano plasma COD sensors and its detection method Download PDFInfo
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Abstract
The present invention relates to a kind of visible light catalytic nano plasma COD sensors and its detection method, COD sensors are formed by visible light catalyst and nano plasma, it is catalyzed using visible light catalyst and produces hydroxyl radical free radical and peroxy radical oxidation of organic compounds, in-situ investigation is carried out to catalysis oxidation using nanometer plasma resonance body simultaneously, so as to realize COD measure.Quick catalysis is aoxidized and is combined with highly sensitive sensing by the COD sensors of the present invention, reflect that oxidation rate is disturbed in the absence of signal background by plasma resonance vibration frequency, detection range is wide, signal to noise ratio is high, interference resistance is strong and long working life, suitable for ambient scene monitoring and the online COD of water process measure.
Description
Technical field
The present invention relates to a kind of COD sensors, more particularly to one kind based on visible light catalytic oxidation Organic substance in water, same
Shi Liyong nanometer plasmas resonance body carries out the COD sensors of in-situ investigation.
Background technology
COD（COD）Refer to aoxidize water body in organic matter consume corresponding oxygen concentration, reflect water body by
The degree of Organic Pollution, it is the primary parameter that water environment monitoring and water analysis must survey.The standard method of existing COD measure has
Two kinds of potassium dichromate method and permanganimetric method, both are both needed to carry out oxidation operation under 100 DEG C of high temperature above, during energy charge,
And be both needed to consume the venomous injurant such as substantial amounts of heavy metallic salt and strong acid/base, cause secondary pollution.Therefore, urged based on new
Change oxidation system, exploitation low energy consumption, the COD sensors of non-secondary pollution turn into the important development direction of water monitoring technology.
The COD sensors of Recent study, mainly using electro-catalysis, photocatalysis and the class oxidation system of photoelectrocatalysis three, pass
Sensor signal reflects catalysis oxidation speed, is the directly proportional detections for realizing COD of COD based on oxidation operation speed and its concentration.
Chinese invention patent application such as publication number CN101929980A discloses a kind of three-dimensional microstructures electro-catalysis using cupric oxide
COD compound sensors, notification number CN101509886B Chinese invention patent are disclosed one kind and received using the short titanium dioxide of titanium-based
The ultraviolet light electrocatalytic chemical oxygen demand (COD) sensor of mitron array.Existing photocatalysis and photoelectrocatalysis COD sensor technologies, main use are received
Rice semi-conducting material excites the valence-band electrons of lower semiconductor to transit to conduction band, produces electron-hole as catalyst in illumination
It is right, most organic matters can be aoxidized at normal temperatures.But prior art there is problems：Firstly, since most of partly lead
Greater band gap between body valence band and conduction band, it is that ultraviolet light of the wavelength less than 400nm can just excite its valence band electric only compared with energy height
Son；Secondly, there is the background signal of certain non-photochemical catalytic oxidation in COD working sensors, cause to be difficult to fundamentally improve COD
The signal to noise ratio of sensor, COD measure is set larger error to be present；Finally, nano-photocatalyst has extremely strong adsorption capacity, favourable
While oxidation operation, also easily cause catalyst by Organic Pollution, the normal response of severe jamming COD sensors,
It can not even work.These above-mentioned defects seriously constrain the popularization and application of COD sensors.
The content of the invention
An object of the present invention is to provide a kind of COD sensors to reduce illumination requirement, improve signal to noise ratio and use
Life-span, a further object of the present invention are the COD sensor detecting methods for providing a kind of matching.
In order to realize first purpose, the present invention provides a kind of visible light catalytic nano plasma COD sensors, by saturating
Bright substrate and the film that is arranged in the transparent substrates are formed, the film by visible light catalyst, nanostructured conductor with
And inert material coating is formed, the visible light catalyst produces the inorganic material of hydroxyl radical free radical and peroxy radical for catalysis
Material, the nanostructured conductive surface have the free electron set as nano plasma, and the inert material coating is
The inorganic or polymer material layer mechanically and chemically protected is provided for visible light catalyst and nanostructured conductor.
Above-mentioned visible light catalyst is nano inorganic material, can be nano plasma or nanometer plasma
The compound of body and light-sensitive material or semiconductor, light-sensitive material include silver salt such as silver halide, semiconductor for example silicon, germanium, GaAs,
Titanium dioxide etc., the material of inert material coating can be silica or polymethacrylates etc.,.
Further, it is seen that photochemical catalyst is the combination of simple substance, compound or any two or more simple substance or compound, institute
Nanostructured conductor is stated as elemental metals or the mixture of two or more simple substance, its size includes size appointing in below 100nm
Meaning configurational unit and combinations thereof, such as nanoparticle, nanotube, nanometer rods, nuclear shell structure nano grain.
Further, the visible light catalyst and nanostructured conductor are same materials.
Further, the film is at least one layer, and the gross thickness of film is less than 0.1mm.
In order to realize second purpose, the present invention provides a kind of inspection of visible light catalytic nano plasma COD sensors
Survey method, including have the following steps：
1）In various criterion concentration C OD detection cells, COD sensors are put into；
2）In various criterion concentration C OD detection cells, add as hydroxyl radical free radical and the substrate in peroxy radical source,
The visible light catalyst catalysis substrate, which produces hydroxyl radical free radical and peroxy radical, makes oxidation operation；The nanometer plasma
Resonance body carries out in-situ investigation to photochemical catalytic oxidation；
3）The COD sensors in various criterion concentration C OD detection cells are continuously detected using ultraviolet-visible spectrum,
Gather COD sensor signals simultaneously；
4）Draw COD solution concentrations and the linear relationship chart of COD sensor signal undulations change；
5）Treat the COD solution repeat step 1 of detectable concentration）、2）With 3）, corresponding COD sensor signals are obtained, according to
Step 4）COD solution concentrations corresponding to obtaining.
Wherein, nanometer plasma resonance body is that nano plasma absorbs the generation resonance of specific wavelength visible ray, is shown
Characteristic spectrum absorbs；In-situ investigation is based on electron exchange of the nanometer plasma resonance body to adjacent catalyst in catalysis oxidation
Periodically change is synchronously made to fluctuate.
Further, the sensor signal is to describe the arbitrary parameter of plasma characteristics spectral absorption, including certain wave
Long absorbance, peak position, peak height and the curvature of absworption peak.
Further, the substrate is water and dissolved oxygen, and substrate and COD molar concentration rate are more than 0.5, to ensure substrate mistake
Amount.
The characteristics of above-mentioned technical proposal is：In the substrate of visible transparent such as glass, it will be seen that photochemical catalyst and nanometer
Fixed film is made in plasma, the wet methods such as self assembly, spin coating can be used to prepare, and can also use the dry method such as vapour deposition
Prepare, preparation can also be combined with dry method using wet method.During detection, COD sensors are using visible light catalyst in visible ray
Under irradiation, band-to-band transition occurs for its valence-band electrons, produces light induced electron (e-) and hole (h+).Electronics (e-) is adsorbed in nanometer
Grain surface dissolved oxygen trapped electron formed superoxide anion, and hole (h+) by adsorb catalyst surface hydroxide ion
Hydroxyl free radical is melted into water oxygen.Superoxide anion and hydroxyl free radical have very strong oxidisability, can have most of
Machine thing is oxidizing to final product CO2And H2O.During photochemical catalytic oxidation detects COD, it is special that nano plasma is carried out in real time
The measurement of spectral absorption is levied, obtains sensor signal；Can be in the certain wave strong point i.e. measure of Single wavelength absorbance, can also
It is the measure of a wavelength range absorption spectrum.Because photochemical catalytic oxidation speed to organic concentration is COD directly proportional, therefore can
By observing photochemical catalytic oxidation velocity determination COD；Photochemical catalytic oxidation speed, it is equal to the circulation rate of catalyst receiving and losing electrons,
Can be to obtain in the vibration frequency of sensor signal or cycle by nanometer plasma resonance body.
The COD sensor technologies of the present invention, can be measured, in the absence of secondary pollution at normal temperatures；And with existing COD
Sensor technology is compared, and is had the following advantages and effect：
First, the present invention utilizes the visible light catalytic oxidation organic matter of ultraviolet-visible spectrometer, it is not necessary to additional other energy
Amount.
Secondly, the present invention carries out in-situ investigation using nano plasma, and reflection catalysis oxidation speed is sensor letter
Number fluctuation frequency rather than sensor signal or its change size, the background and interference signal of non-catalytic oxidation do not interfere with
To the frequency of sensor signal undulations, therefore sensor has high signal to noise ratio and good anti-interference, misses COD measure
Difference is small, accuracy is high.
Finally, sensor of the invention, inert material protection activity material can be used, active material is urged for visible ray herein
Agent and nano plasma, polluted so as to avoid sensor from being adsorbed by organic matter；Although the introducing of protection materials may here
The sensitivity of sensor is reduced, but because nano plasma sensing has high sensitivity, makes the sensitive of sacrifice sensor
Degree efficiently solves sensor because absorption pollution makes the short difficulty of its working life to ensure that the normal work of sensor is possibly realized
Topic.
The visible light catalytic nano plasma COD sensors of the present invention, have signal to noise ratio height, interference resistance strong and work
The advantages that long lifespan, suitable for ambient scene monitoring and the online COD of water process measure, it is with a wide range of applications.
Brief description of the drawings
Fig. 1 is the COD sensor construction schematic diagrames of Example 1 and Example 2 of the present invention；
In Fig. 2（A）、（B）For the stereoscan photograph of the COD colorimetric sensor films of Example 1 and Example 2 of the present invention；
Fig. 3 is the COD detecting system schematic diagrams of Example 1 and Example 2 of the present invention；
Fig. 4 is detection cell schematic diagram in the COD detecting systems of Example 1 and Example 2 of the present invention；
In Fig. 5（A）、（B）For the COD sensor visible absorption spectra figures of the embodiment 2 of the embodiment of the present invention 1；
In Fig. 6（A）、（B）For the COD sensor signal undulations figures of the embodiment 2 of the embodiment of the present invention 1；
In Fig. 7（A）、（B）For the COD linear sensor figures of the embodiment 2 of the embodiment of the present invention 1.
Embodiment
The present invention is further detailed explanation with reference to the accompanying drawings and detailed description：
Embodiment 1：
The visible light catalytic nano plasma COD sensors formed with silver chlorate-Nano silver grain.
1）It is prepared by sensor
Fig. 1 is the sensor construction schematic diagram of the present embodiment, and 1 is substrate of glass in figure, and 2 be silver chlorate-Nano silver grain.
1ml 100mM silver nitrate solutiones are taken in container, 3ml deionized waters and 10mg polyvinylpyrrolidones are added, in magnetic agitation
Under the conditions of be slowly added to 1ml 100mM sodium chloride solutions, be fully mixed to after milky chlorination silver sol formed, rapidly join
200ul 1M tris solutions, are transferred quickly to uviol lamp（254nm, 8W）Under, it is lasting to stir, stop after 10min
Only react, gained suspension is centrifuged, collect precipitation, and after cleaning ten times with deionized water, dry 12h at 60 DEG C, produce chlorine
Change silver-Nano silver grain composite photo-catalyst.
Wherein mM is mmol/L.
Substrate is used glass as, substrate of glass is respectively placed in ultrasonic 1h in acetone, ethanol, supersonic frequency 40KHz-
42KHz carries out surface clean；It is subsequently dipped to the Piranha solution of fresh configuration（H2SO4:H2O2=3:1）In do further it is hydrophilic
Change is handled.
Nano silver grain obtained above/silver chlorate composite photo-catalyst is dispersed in water (2mg/ml), is directly added dropwise
Continue to be added dropwise after drying on the glass substrate, prepare four layers repeatedly, it is compound that 200ul Nano silver grains/silver chlorate is added dropwise in first layer
Photocatalyst dispersion liquid, second and third, four layers 400ul Nano silver grains/silver chlorate composite photocatalyst agent dispersing liquid is added dropwise respectively.
Most film is annealed 30 minutes at 300 DEG C and produces silver chlorate-Nano silver grain COD sensors at last.Its stereoscan photograph is such as
Shown in Fig. 2 (A).
2）COD is detected
By 1）In obtained sensor coordinate miniature ultraviolet-visible spectrometer to carry out COD detections, detecting system schematic diagram
As shown in Figure 3.
As shown in Fig. 4 (A), 1 is detection cell in figure, and using commercial clear glass cuvette, 2 be COD sensors；Will
Sensor is positioned in detection cell, determinand and appropriate amount of deionized water is injected into detection cell, this sentences 0~20mg/L neighbours benzene two
Formic acid hydrogen potassium solution is determinand as COD standard liquid.
Detection architecture is continuously detected using miniature ultraviolet-visible spectrum, while carries out data sampling and processing, can
See that abosrption spectrogram is as shown in Figure 5.
As shown in Fig. 6 (A), by recording the COD solution of the various concentrations caused sensor signal in detection process
Fluctuating change, the linear relationship of the two is established, as shown in Fig. 7 (A), so as to reach the purpose detected to COD.
Embodiment 2：
The visible light catalytic nano plasma COD sensors formed with nano titanium oxide-nanogold.
1）It is prepared by sensor
Fig. 1 is the sensor construction schematic diagram of the present embodiment, and 1 be substrate of glass in the figure, and 2 be nano titanium oxide-receive
The golden visible light catalytic nano plasma of rice.
Weigh 0.08g TiO2Nano material is dispersed in 10ml deionized waters, ultrasound 5 minutes to form uniform dispersion,
24uL 4%（w/w）HAuCl4 storing solutions to TiO2 dispersions, continuing magnetic force stirs 5min；0.0012g ascorbic acid is weighed to add
Enter in system, under the conditions of Hg lamp irradiation, lasting stirring reduction 30min；Obtained sample is centrifuged, cleans 3 times, disperses again
Nano titanium oxide-nanogold dispersion liquid is produced into 10mL deionized waters.
Substrate is used glass as, substrate of glass is respectively placed in ultrasonic 1h in acetone, ethanol, supersonic frequency 40KHz-
42KHz, carry out surface clean；It is subsequently dipped to the Piranha solution of fresh configuration（H2SO4:H2O2=3:1）In do further it is hydrophilic
Change is handled.
Nano titanium oxide-nanogold dispersion liquid is spun in the substrate of glass after hydrophilicity-imparting treatment, annealed at 500 DEG C
Produce within 30 minutes the visible light catalytic nano plasma COD sensors that nano titanium oxide-nanogold is formed, COD sensors
Shown in the transmission electron microscope photo of film such as Fig. 2 (B).
2）COD is detected
By 1）In obtained sensor coordinate miniature ultraviolet-visible spectrometer to carry out COD detections, detecting system schematic diagram
As shown in Figure 3.
As shown in Fig. 4 (B), 1 is detection cell in figure, and using commercial clear glass cuvette, 2 be COD sensors, 3
For cycles samples access way；Sensor is positioned in detection cell, and determinand is injected into detection cell (with 0~20mg/L neighbour's benzene
Standard liquid of the dioctyl phthalate hydrogen potassium solution as COD) and appropriate amount of deionized water.
Detection architecture is continuously detected using miniature ultraviolet-visible spectrum, while carries out data sampling and processing, can
See shown in abosrption spectrogram such as Fig. 5 (B).
By recording COD solution caused sensor signal undulations change in detection process of various concentrations, obtain
Signal wave cardon shown in Fig. 6 (B), establishes the linear relationship of the two, the COD linear graphs as shown in Fig. 7 (B) is obtained, so as to reach
The purpose detected to COD.
Above-described is only the preferred embodiment of the present invention, and the general knowledge such as known concrete structure and characteristic exists in scheme
This is not described excessively.It should be pointed out that for those skilled in the art, before structure and method of the present invention is not departed from
Put, several modifications and improvements can also be made, these should also be considered as protection scope of the present invention, and these are all without influence sheet
Invent the effect and practical applicability implemented.
Claims (3)
1. the detection method of visible light catalytic nano plasma COD sensors, it is characterised in that including having the following steps：
1）In various criterion concentration C OD detection cells, COD sensors are put into；
2）In various criterion concentration C OD detection cells, add as hydroxyl radical free radical and the substrate in peroxy radical source, it is described
Visible light catalyst catalysis substrate, which produces hydroxyl radical free radical and peroxy radical, makes oxidation operation；The nano plasma is total to
Shake and in-situ investigation is carried out to photochemical catalytic oxidation；
3）The COD sensors in various criterion concentration C OD detection cells are continuously detected using ultraviolet-visible spectrum, simultaneously
Gather COD sensor signals；
4）Draw COD solution concentrations and the linear relationship chart of COD sensor signal undulations change；
5）Treat the COD solution repeat step 1 of detectable concentration）、2）With 3）, corresponding COD sensor signals are obtained, according to step
4）COD solution concentrations corresponding to obtaining；
The COD sensors arrived used in the detection method of above-mentioned visible light catalytic nano plasma COD sensors are visible
Photocatalytic nanometer plasma COD sensors；The visible light catalytic nano plasma COD sensors by transparent substrates and
The film being arranged in the transparent substrates is formed, and the film is by visible light catalyst, nanostructured conductor and inert material
Coating is formed, and the visible light catalyst produces the inorganic material of hydroxyl radical free radical and peroxy radical for catalysis, described to receive
There is the free electron set as nano plasma on rice configuration conductor surface, and the inert material coating is urged for visible ray
Agent and nanostructured conductor provide the inorganic or polymer material layer mechanically and chemically protected.
2. the detection method of sensor according to claim 1, it is characterised in that the sensor signal for description etc. from
The parameter that daughter characteristic spectrum absorbs, include the absorbance of specific wavelength, peak position, peak height and the curvature of absworption peak.
3. the detection method of sensor according to claim 1, it is characterised in that the substrate is water and dissolved oxygen, bottom
Thing and COD molar concentration rate are more than 0.5, to ensure substrate excess.
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