CN104697945A - Visible-light catalytic nano plasma COD sensor and detection method thereof - Google Patents
Visible-light catalytic nano plasma COD sensor and detection method thereof Download PDFInfo
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- CN104697945A CN104697945A CN201510048430.5A CN201510048430A CN104697945A CN 104697945 A CN104697945 A CN 104697945A CN 201510048430 A CN201510048430 A CN 201510048430A CN 104697945 A CN104697945 A CN 104697945A
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Abstract
The invention relates to a visible-light catalytic nano plasma COD sensor and a detection method thereof. The COD sensor is composed of a visible light catalyst and a nano plasma; and by using the catalysis of the visible light catalyst, hydroxyl radical and peroxy radical oxidized organic compounds are produced, and meanwhile, in-situ detection is performed on catalytic oxidation by using the resonance of the nano plasma, so that the determination on COD is realized. According to the COD sensor disclosed by the invention, rapid catalytic oxidation and high-sensitivity sensing are combined, and through the resonance fluctuation frequency of the plasma, a situation that the oxidation rate cannot be influenced by signal background interference is reflected, so that the COD sensor is wide in detection range, high in signal-to-noise ratio, strong in interference resistance and long in service life, furthermore, the COD sensor is applicable to the environmental field monitoring and the on-line COD determination in water treatment.
Description
Technical field
The present invention relates to a kind of COD sensor, particularly relate to a kind of based on visible light catalytic oxidation Organic substance in water, utilize nanometer plasma resonance body to carry out the COD sensor of in-situ investigation simultaneously.
Background technology
Chemical oxygen demand (COD) (COD) refers to that in oxidation water body, organism institute consumes corresponding oxygen concentration, reflects the degree that water body is subject to Organic Pollution, is the primary parameter that water environment is monitored and water analysis must be surveyed.The standard method that existing COD measures has potassium dichromate method and permanganimetric method two kinds, both all need carry out oxidation operation under high temperature more than 100 DEG C, during energy charge, and all need to consume the venomous injurant such as a large amount of heavy metallic salts and strong acid/alkali, cause secondary pollution.Therefore, based on new catalytic oxidation system, the COD sensor of exploitation low energy consumption, non-secondary pollution becomes the important development direction of water monitoring technology.
The COD sensor of Recent study, mainly utilizes electro-catalysis, photocatalysis and photoelectrocatalysis three class oxidation system, sensor signal reflection catalytic oxidation speed, and being directly proportional to its concentration and COD based on oxidation operation speed realizes the detection of COD.Chinese invention patent application as publication number CN101929980A discloses a kind of electrocatalytic chemical oxygen demand (COD) compound sensor with three-dimensional microstructure utilizing cupric oxide, and the Chinese invention patent of notification number CN101509886B discloses a kind of ultraviolet light electrocatalytic chemical oxygen demand (COD) sensor utilizing the short Nano tube array of titanium dioxide of titanium base.Existing photocatalysis and photoelectrocatalysis COD sensor technology, the main nano semiconductor material that adopts, as catalyzer, excites the valence-band electrons of lower semiconductor to transit to conduction band in illumination, produces electron-hole pair, can be oxidized most organism at normal temperatures.But prior art also exists following problem: first, due to the greater band gap between most of semiconductor valence band and conduction band, only have the ultraviolet light being less than 400nm compared with energy height and wavelength just can excite its valence-band electrons; Secondly, there is the background signal of certain non-photochemical catalytic oxidation in COD working sensor, causes the signal to noise ratio (S/N ratio) being difficult to fundamentally improve COD sensor, COD measured and there is comparatively big error; Finally, nano-photocatalyst has extremely strong adsorptive power, and while being conducive to oxidation operation, also easily cause catalyzer by Organic Pollution, the normal response of severe jamming COD sensor, even cannot work.These defects above-mentioned seriously constrain applying of COD sensor.
Summary of the invention
An object of the present invention is to provide a kind of COD sensor to reduce illumination requirement, to improve signal to noise ratio (S/N ratio) and serviceable life, and another object of the present invention is the COD sensor detecting method providing a kind of coupling.
In order to realize first object, the invention provides a kind of visible light catalytic nano plasma COD sensor, be made up of transparent substrates and the film be arranged in this transparent substrates, described film is by visible light catalyst, nanostructured conductor and inert material overlayer are formed, described visible light catalyst is the inorganic material that catalysis produces hydroxyl radical free radical and peroxy radical, described nanostructured conductive surface has the free electron set as nano plasma, described inert material overlayer is for visible light catalyst and nanostructured conductor provide machinery and chemoprotectant inorganic or polymer material layer.
Above-mentioned visible light catalyst is nano inorganic material, it can be nano plasma, also can be the compound of nano plasma and photochromics or semiconductor, photochromics comprises silver salt if silver halide, semiconductor are as silicon, germanium, gallium arsenide, titania etc., the tectal material of inert material can be silicon dioxide or polymethacrylate etc..
Further, visible light catalyst is the combination of simple substance, compound or any two or more simple substance or compound, described nanostructured conductor is the potpourri of elemental metals or two or more simple substance, its size comprises size in the arbitrary configuration unit of below 100nm and combination thereof, as nanoparticle, nanotube, nanometer rods, nuclear shell structure nano grain etc.
Further, described visible light catalyst and nanostructured conductor are commaterials.
Further, described film is at least one deck, and the gross thickness of film is less than 0.1mm.
In order to realize second object, the invention provides a kind of detection method of visible light catalytic nano plasma COD sensor, including following steps:
1) in various criterion concentration C OD detection cell, COD sensor is put into;
2) in various criterion concentration C OD detection cell, add the substrate as hydroxyl radical free radical and peroxy radical source, described visible light catalyst catalytic substrate produces hydroxyl radical free radical and peroxy radical makes oxidation operation; Described nanometer plasma resonance body carries out in-situ investigation to photochemical catalytic oxidation;
3) utilize ultraviolet-visible spectrum to carry out continuous detecting to the COD sensor in various criterion concentration C OD detection cell, gather COD sensor signal simultaneously;
4) linear relationship chart that COD solution concentration and COD sensor signal undulations change is drawn;
5) the COD solution treating detectable concentration repeats step 1), 2) and 3), obtain corresponding COD sensor signal, obtain corresponding COD solution concentration according to step 4).
Wherein, nanometer plasma resonance body is that nano plasma absorbs specific wavelength visible ray generation resonance, shows characteristic spectrum and absorbs; In-situ investigation synchronously makes periodic change based on nanometer plasma resonance body to the electron exchange of adjacent catalyst when catalytic oxidation to fluctuate.
Further, described sensor signal is the arbitrary parameter describing plasma characteristics spectral absorption, comprises the absorbance of specific wavelength, the peak position of absorption peak, peak height and curvature.
Further, described substrate is water and dissolved oxygen DO, and the molar concentration rate of substrate and COD is greater than 0.5, to ensure that substrate is excessive.
The feature of technique scheme is: in the substrate of visible transparent as on glass, visible light catalyst and nano plasma are made fixing film, the wet-layer preparation such as self assembly, spin coating can be adopted, also can adopt the dry processes such as vapour deposition, wet method can also be adopted to combine with dry method and prepare.During detection, COD sensor utilizes visible light catalyst under visible light illumination, its valence-band electrons generation interband transition, produces light induced electron (e-) and hole (h+).The dissolved oxygen DO trapped electron that electronics (e-) is adsorbed on nano grain surface forms superoxide anion, and the hydroxide ion being adsorbed on catalyst surface is become hydroxyl free radical with Water oxidize by hole (h+).Superoxide anion and hydroxyl free radical have very strong oxidisability, can by the oxidation operation of the overwhelming majority to final product CO
2and H
2o.Detect in photochemical catalytic oxidation in the process of COD, carry out the measurement of nano plasma characteristic spectrum absorption in real time, obtain sensor signal; Can be the mensuration in certain wave strong point and Single wavelength absorbance, also can be the mensuration of a wavelength range absorption spectrum.Because photochemical catalytic oxidation speed is directly proportional to organic concentration and COD, therefore by observation photochemical catalytic oxidation velocity determination COD; Photochemical catalytic oxidation speed, is equal to the rate of circulation of catalyzer receiving and losing electrons, can be obtained by the vibration frequency of nanometer plasma resonance body and sensor signal or cycle.
COD sensor technology of the present invention, can measure at normal temperatures, there is not secondary pollution; And compared with existing COD sensor technology, there is following advantage and effect:
First, the present invention utilizes the visible light catalytic oxidation organism of ultraviolet-visible spectrometer, does not need other energy additional.
Secondly, the present invention utilizes nano plasma to carry out in-situ investigation, what reflect catalytic oxidation speed is the frequency of sensor signal undulations but not the size of sensor signal or its change, the background of non-catalytic oxidation and undesired signal can not have influence on the frequency of sensor signal undulations, therefore sensor has high signal to noise ratio (S/N ratio) and good anti-interference, makes that COD error at measurment is little, accuracy is high.
Finally, sensor of the present invention, can adopt inert material prolection material, active material is visible light catalyst and nano plasma herein, thus avoids sensor to be polluted by Adsorption of Organic; Although the introducing of protective material may reduce the sensitivity of sensor here; but because nano plasma sensing has high sensitivity; make the sensitivity of sacrifice sensor to ensure that the normal work of sensor becomes possibility, efficiently solve the difficult problem that sensor makes its mission life short because of adsorption fouling.
Visible light catalytic nano plasma COD sensor of the present invention, has that signal to noise ratio (S/N ratio) is high, an advantage such as the strong and long working life of interference resistance, is applicable to the mensuration of ambient scene monitoring and the online COD of water treatment, is with a wide range of applications.
Accompanying drawing explanation
Fig. 1 is the COD sensor construction schematic diagram of the embodiment of the present invention 1 and embodiment 2;
The stereoscan photograph of the COD colorimetric sensor films that (A) in Fig. 2, (B) are the embodiment of the present invention 1 and embodiment 2;
Fig. 3 is the COD detection system schematic diagram of the embodiment of the present invention 1 and embodiment 2;
Fig. 4 is detection cell schematic diagram in the COD detection system of the embodiment of the present invention 1 and embodiment 2;
The COD sensor visible absorption spectra figure that in Fig. 5, (A), (B) are the embodiment of the present invention 1 embodiment 2;
The COD sensor signal undulations figure that in Fig. 6, (A), (B) are the embodiment of the present invention 1 embodiment 2;
The COD linear sensor figure that in Fig. 7, (A), (B) are the embodiment of the present invention 1 embodiment 2.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation:
Embodiment 1:
The visible light catalytic nano plasma COD sensor formed with silver chloride-Nano silver grain.
1) sensor preparation
Fig. 1 is the sensor construction schematic diagram of the present embodiment, and in figure, 1 is substrate of glass, and 2 is silver chloride-Nano silver grain.Get 1ml 100mM liquor argenti nitratis ophthalmicus in container, add 3ml deionized water and 10mg polyvinylpyrrolidone, 1ml 100mM sodium chloride solution is slowly added under magnetic agitation condition, be fully mixed to after milky silver chloride colloidal sol formed, add 200ul 1M tris solution fast, be transferred to rapidly uviol lamp (254nm, 8W), Keep agitation, stops reaction after 10min, by centrifugal for gained suspension, collecting precipitation, and with after washed with de-ionized water ten times, at 60 DEG C, dry 12h, obtain silver chloride-Nano silver grain composite photo-catalyst.
Wherein mM is mmol/L.
Use glass as substrate, substrate of glass is placed in respectively acetone, the ultrasonic 1h of ethanol, ultrasonic frequency 40KHz-42KHz carries out surface clean; Immerse the Piranha solution (H of fresh configuration subsequently
2sO
4: H
2o
2=3:1) in do further hydrophilicity-imparting treatment.
Above-mentioned obtained Nano silver grain/silver chloride composite photo-catalyst is dispersed in water (2mg/ml), direct dropping continues after drying on the glass substrate to drip, repeatedly prepare four layers, ground floor drips 200ul Nano silver grain/silver chloride composite photocatalyst agent dispersing liquid, second and third, four layers drip 400ul Nano silver grain/silver chloride composite photocatalyst agent dispersing liquid respectively.Film is annealed and within 30 minutes, is namely obtained silver chloride-Nano silver grain COD sensor at 300 DEG C the most at last.Its stereoscan photograph is as shown in Fig. 2 (A).
2) COD detects
By 1) in obtained sensor coordinate miniature ultraviolet-visible spectrometer to carry out COD detection, detection system schematic diagram is as shown in Figure 3.
As shown in Fig. 4 (A), in figure, 1 is detection cell, and adopt commercial clear glass cuvette, 2 is COD sensor; Be positioned over by sensor in detection cell, inject determinand and appropriate amount of deionized water in detection cell, this sentences 0 ~ 20mg/L Potassium Hydrogen Phthalate solution as the standard solution of COD is determinand.
Utilize miniature ultraviolet-visible spectrum to carry out continuous detecting to detection system, carry out data sampling and processing simultaneously, visible absorption spectra figure as shown in Figure 5.
As shown in Fig. 6 (A), the sensor signal undulations change brought in testing process by the COD solution recording variable concentrations, the linear relationship of both foundation, as shown in Fig. 7 (A), thus reaches the object detected COD.
Embodiment 2:
The visible light catalytic nano plasma COD sensor formed with nano titanium oxide-nm of gold.
1) sensor preparation
Fig. 1 is the sensor construction schematic diagram of the present embodiment, and in this figure, 1 is substrate of glass, and 2 is nano titanium oxide-nm of gold visible light catalytic nano plasma.
Take 0.08g TiO
2nano material is dispersed in 10ml deionized water, ultrasonic 5 minutes to form uniform dispersion, 24uL 4%(w/w) HAuCl4 storing solution to TiO2 dispersed system, continuing magnetic force stir 5min; Taking 0.0012g ascorbic acid adds in system, under Hg lamp irradiation condition, and Keep agitation reduction 30min; By centrifugal for obtained sample, clean 3 times, be again dispersed in 10mL deionized water and namely obtain nano titanium oxide-nm of gold dispersion liquid.
Use glass as substrate, substrate of glass is placed in respectively acetone, the ultrasonic 1h of ethanol, ultrasonic frequency 40KHz-42KHz, carries out surface clean; Immerse the Piranha solution (H of fresh configuration subsequently
2sO
4: H
2o
2=3:1) in do further hydrophilicity-imparting treatment.
Nano titanium oxide-nm of gold dispersion liquid is spun in the substrate of glass after hydrophilicity-imparting treatment, at 500 DEG C, namely annealing obtain the visible light catalytic nano plasma COD sensor that nano titanium oxide-nm of gold is formed for 30 minutes, and the transmission electron microscope photo of COD colorimetric sensor films is as shown in Fig. 2 (B).
2) COD detects
By 1) in obtained sensor coordinate miniature ultraviolet-visible spectrometer to carry out COD detection, detection system schematic diagram is as shown in Figure 3.
As shown in Fig. 4 (B), in figure, 1 is detection cell, and adopt commercial clear glass cuvette, 2 is COD sensor, and 3 is cycles samples access way; Sensor is positioned in detection cell, injects determinand (using 0 ~ 20mg/L Potassium Hydrogen Phthalate solution as the standard solution of COD) and appropriate amount of deionized water in detection cell.
Utilize miniature ultraviolet-visible spectrum to carry out continuous detecting to detection system, carry out data sampling and processing simultaneously, visible absorption spectra figure is as shown in Fig. 5 (B).
The sensor signal undulations change brought in testing process by the COD solution recording variable concentrations, obtain signal wave cardon shown in Fig. 6 (B), the linear relationship of both foundation, obtain the COD linear graph as shown in Fig. 7 (B), thus reach the object that COD is detected.
Above-described is only the preferred embodiment of the present invention, and in scheme, the general knowledge such as known concrete structure and characteristic does not do too much description at this.Should be understood that; for a person skilled in the art, under the prerequisite not departing from structure and method of the present invention, some distortion and improvement can also be made; these also should be considered as protection scope of the present invention, and these all can not affect effect of the invention process and practical applicability.
Claims (7)
1. a visible light catalytic nano plasma COD sensor, it is characterized in that: be made up of transparent substrates and the film be arranged in this transparent substrates, described film is by visible light catalyst, nanostructured conductor and inert material overlayer are formed, described visible light catalyst is the inorganic material that catalysis produces hydroxyl radical free radical and peroxy radical, described nanostructured conductive surface has the free electron set as nano plasma, described inert material overlayer is for visible light catalyst and nanostructured conductor provide machinery and chemoprotectant inorganic or polymer material layer.
2. visible light catalytic nano plasma COD sensor according to claim 1, it is characterized in that: visible light catalyst is the combination of simple substance, compound or any two or more simple substance or compound, described nanostructured conductor is the potpourri of elemental metals or two or more simple substance, and its size comprises size in the arbitrary configuration unit of below 100nm and combination thereof.
3. visible light catalytic nano plasma COD sensor according to claim 1, is characterized in that: described visible light catalyst and nanostructured conductor are commaterials.
4. visible light catalytic nano plasma COD sensor according to claim 1, it is characterized in that: described film is at least one deck, the gross thickness of film is less than 0.1mm.
5. a detection method for visible light catalytic nano plasma COD sensor as claimed in claim 1, is characterized in that including following steps:
1) in various criterion concentration C OD detection cell, COD sensor is put into;
2) in various criterion concentration C OD detection cell, add the substrate as hydroxyl radical free radical and peroxy radical source, described visible light catalyst catalytic substrate produces hydroxyl radical free radical and peroxy radical makes oxidation operation; Described nanometer plasma resonance body carries out in-situ investigation to photochemical catalytic oxidation;
3) utilize ultraviolet-visible spectrum to carry out continuous detecting to the COD sensor in various criterion concentration C OD detection cell, gather COD sensor signal simultaneously;
4) linear relationship chart that COD solution concentration and COD sensor signal undulations change is drawn;
5) the COD solution treating detectable concentration repeats step 1), 2) and 3), obtain corresponding COD sensor signal, obtain corresponding COD solution concentration according to step 4).
6. sensor detecting method according to claim 5, is characterized in that: described sensor signal is the arbitrary parameter describing plasma characteristics spectral absorption, comprises the absorbance of specific wavelength, the peak position of absorption peak, peak height and curvature.
7. sensor detecting method according to claim 5, is characterized in that: described substrate is water and dissolved oxygen DO, and the molar concentration rate of substrate and COD is greater than 0.5, to ensure that substrate is excessive.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111812162A (en) * | 2020-06-23 | 2020-10-23 | 武汉工程大学 | Acetone gas sensor excited by visible light and preparation method thereof |
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| CN102161732A (en) * | 2006-01-13 | 2011-08-24 | 电气化学工业株式会社 | Curable resin composition, surface protection method, temporary fixation method, and separation method |
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Patent Citations (5)
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| JP2000189796A (en) * | 1999-01-01 | 2000-07-11 | Toto Ltd | Member having photocatalytic function |
| CN102161732A (en) * | 2006-01-13 | 2011-08-24 | 电气化学工业株式会社 | Curable resin composition, surface protection method, temporary fixation method, and separation method |
| CN101285790A (en) * | 2008-04-25 | 2008-10-15 | 中国科学院长春应用化学研究所 | Nanometer TiO2 nanometer thin film sensing electrode preparation method |
| CN102909008A (en) * | 2012-10-26 | 2013-02-06 | 湖北工业大学 | Preparation method for TiO2/SiO2-Ag-SiO2 nanocomposite film |
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Non-Patent Citations (12)
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111812162A (en) * | 2020-06-23 | 2020-10-23 | 武汉工程大学 | Acetone gas sensor excited by visible light and preparation method thereof |
| CN111812162B (en) * | 2020-06-23 | 2022-12-09 | 武汉工程大学 | Acetone gas sensor excited by visible light and preparation method thereof |
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