CN108387526A - A kind of PhotoelectrochemicalMethod Method of highly sensitive detection nitrogen dioxide - Google Patents
A kind of PhotoelectrochemicalMethod Method of highly sensitive detection nitrogen dioxide Download PDFInfo
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- G01N21/1702—Systems in which incident light is modified in accordance with the properties of the material investigated with opto-acoustic detection, e.g. for gases or analysing solids
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Abstract
The present invention discloses a kind of PhotoelectrochemicalMethod Method of highly sensitive detection nitrogen dioxide, includes the following steps：Synthesize SiO2Microballoon prepares SiO as template2@TiO2Microballoon, TiO2TiO is adulterated with nanometer Ag2Hollow ball obtains nanometer Ag doping TiO2Hollow ball modifies ITO electrode, by this electrode for being detected in the acid PBS buffer solution of various concentration nitrogen dioxide；The TiO that nanometer Ag is adulterated according to content of nitrogen dioxide2Hollow ball modifies the quantitative effect of ITO electrode photoelectric current, establishes quantitative linearity equation and draws quantitation curves.The detection method of the present invention is simple, easy to operate, at low cost, highly sensitive, and with highly selective.
Description
Technical field
The invention belongs to analyze testing field, and in particular to a kind of PhotoelectrochemicalMethod Method of highly sensitive detection nitrogen dioxide.
Background technology
Nitric oxide and nitrogen dioxide are the major pollutants in air, are the weights to form photochemical fog and acid rain
Want reason.Outside atmosphere nitrogen dioxide is mainly derived from fuel combustion and motor vehicle exhaust emission, indoor nitrogen dioxide main source
It uses and smokes in coal fired stove, gas-cooker, many occupation places include being cleaned, being adopted with the welding of acetylene blowpipe, plating, metal
High-concentration nitrogen dioxide is also can contact in mine, dyestuff manufacture, paint and public place such as garage, ferry boat and skifield.Greatly
Gas is precious resources for the survival of mankind, and the destruction of Atmosphere environment resource is a kind of irreversible procedure, restores good air
Quality pays more costs than Air Pollution prevention and control.Nitrogen oxides in Accurate Determining ambient air is dirty for understanding air
Dye mechanism judges atmospheric pollution level, determines pollution source, carrying out air quality early warning and help to formulate rational city rule
Construction etc. is drawn all to be of great significance.
Currently, the chemically and physically characteristic according to gas has derived many gas detection methods.Such as colorimetric method：The measurement
It is much like that method and chemical test paper measure liquid pH value method.Gas is passed through when measurement in the colorimetric cylinder for having solution reagent,
Then it is tested gas to chemically react with solution, solution colour can change in reaction process, and different gas concentrations is molten
Liquid will present different colors, and control color table can roughly estimate the concentration and type of gas.The measurement method is applicable in
Property it is very wide, but precision is relatively low, is suitable for some gas detections without particular instrument detection method；It is passed based on semiconductor technology
Sensor：The operation principle of the sensor is chemistry, biology and physical characteristic based on semi-conducting material.So being classified as
Learn sensitive semiconductor sensor, bio-sensing semiconductor transducer and physics sensitive semiconductor sensor.It can be used for combustibility
The detection of gas, for certain pernicious gases, detection limit is up to ppm stratification levels；Electrochemical sensor：Electrochemical sensor
Principle is that oxidation or reduction reaction occurs based on tested gas and generates the electric signal directly proportional to gas concentration.Electrochemistry passes
Sensor mensuration is to be applied to the detection technique that detection pernicious gas is most common and most ripe in portable gas detector at present,
Its main feature is that it is small, power consumption is small, it is linear and reproducible, last a long time, but there are cross jamming drawbacks；Non-dispersion infrared is inhaled
Receipts method：According to tested gas to the absorption characteristic of infrared light, absorbed amount of infrared light is detected, you can calculate tested gas
The parameters such as concentration.This method measuring range is big, and precision is high, and can measure multiple gases simultaneously, and cross jamming is not present
Effect, but involve great expense；The surface acoustic wave method and gas chromatography-mass spectrum combination method, quartz resonance that also latest developments are got up
Formula gas sensor mensuration etc., above-mentioned measurement method all achieves certain effect.But since tested gaseous species are various,
Chemical property difference is very big, and a kind of instrument can detection that is not only accurate, economic but also quickly solving specific gas currently not yet
Problem, it is desirable that have higher response sensitivity even more extremely difficult multiple gases.Therefore it provides a kind of highly sensitive detection dioxy
The method for changing nitrogen has great application value.
Invention content
Goal of the invention：Present invention aims in view of the deficiencies of the prior art, provide it is a kind of it is simple, easy to operate, at low cost,
The PhotoelectrochemicalMethod Method of highly selective, highly sensitive detection nitrogen dioxide.
Common nitrogen oxides is nitric oxide and nitrogen dioxide, since nitric oxide is easily oxidized to two in air
Nitrogen oxide, so the present invention detects nitrogen oxides in terms of nitrogen dioxide.
Technical solution：The PhotoelectrochemicalMethod Method of highly sensitive detection nitrogen dioxide of the present invention, includes the following steps：
（1）Synthesize SiO2Microballoon is as template：Successively by the tetraethyl orthosilicate of 3.9 ~ 5.9 mL 99%, 100 ~ 125 mL without
Water-ethanol, 7.0 ~ 11.0 mL ultra-pure waters, 2.98 ~ 4.38 mL, 26% ammonium hydroxide are uniformly mixed, and reaction 5 are stirred at room temperature successively
~7 h；By being centrifugally separating to obtain SiO2Microballoon is used ethyl alcohol and water washing, is then dispersed in ethyl alcohol respectively.
（2）Prepare SiO2@TiO2Microballoon：By the SiO of above-mentioned dispersion in ethanol2Microballoon, 55 ~ 75 mg hydroxy propyl celluloses
Element, 15 ~ 20 mL absolute ethyl alcohols, 10 ~ 14 mL acetonitriles and 0.1 ~ 0.3 mL ammonium hydroxide are sufficiently mixed 8 ~ 10 min；Will contain 0.7 ~
3 ~ 9 mL of ethanol solution of 1.2 mL butyl titanates is added into above-mentioned mixed solution, stirs at least 1 h；By generation
SiO2@TiO2Microballoon centrifuge washing is collected, and after being washed respectively with ethyl alcohol, water, is dispersed in water.
（3）TiO2TiO is adulterated with nanometer Ag2The preparation of hollow ball：By SiO2@TiO2Microballoon is added to 3.2 ~ 4.2 mL
In NaOH solution, 2.5 ~ 4.5 h of heating reflux reaction has etched SiO2After microballoon, TiO is obtained2Hollow ball；By centrifuging, washing
Later, the TiO that will be obtained2Hollow ball is dispersed in silver nitrate solution again, continues stirring until few 5h, is washed by centrifugation, ethyl alcohol
After washing, in-situ reducing silver ion obtains nano Ag particles doping TiO2Then hollow ball is dispersed in water.
（4）Nanometer Ag adulterates TiO2Hollow ball modifies ITO electrode：After ITO electrode is cleaned up, by step（3）It prepares
Nano Ag particles adulterate TiO2Drop coating is saturated in one end of ITO electrode, and in room temperature after hollow ball aqueous solution dilutes 20 ~ 30 times
It is dried under environment；With water rinse, nanometer Ag doping TiO is obtained2Hollow ball modifies ITO electrode.
（5）By above-mentioned steps（4）The nanometer Ag of preparation adulterates TiO2Hollow ball modifies ITO electrode and contains two to various concentration
Nitrogen oxide acidity PBS buffer solution detects；The TiO that nanometer Ag is adulterated according to content of nitrogen dioxide2Hollow ball modifies ITO electrode light
The quantitative effect of electric current establishes quantitative linearity equation and draws quantitation curves.
Further preferably technical solution is the present invention, step（5）The preparation side of the acid PBS buffer solution of middle nitrogen dioxide
Method is：Nitrogen dioxide is passed through in NaOH solution, then with hydrochloric acid conditioning solution to neutrality, the solution is then settled to PBS
In buffer solution；Nitrogen dioxide is converted into equimolar NaNO3, when doing quantitation curves, directly use the NaNO of suitable concentration3Mark
Sample solution establishes working curve.
Preferably, according to containing concentration value being respectively 0,1,2,4,6,8,10,20,40,60,80,100 in PBS buffer solution,
The NaNO of 200,400,600,800,1000,2000,4000 and 6000 pmol/L3To step（5）The TiO of middle nanometer Ag doping2
Hollow ball modifies the influence of ITO electrode photoelectric current, establishes linear equation.
Preferably, step（3）Described in NaOH solution a concentration of 1.0 ~ 2.5 mol/L.
Preferably, step（3）Described in silver nitrate solution a concentration of 0.05 ~ 0.2 mmol/L.
Preferably, step（4）Described in nano Ag particles adulterate TiO2Hollow ball aqueous solution extension rate is 30 times.
Preferably, step（5）Described in acidity PBS pH be 3.0 ~ 4.0.
Advantageous effect：（1）The present invention is based on strong oxidizing property of the nitrogen dioxide under acid system, pass through its oxidation nanometer silver
Unformed titanium dioxide hollow ball is adulterated, Ag is generated2O/Ag/TiO2The concentration of hollow ball, nitrogen dioxide is higher, in acid system
Under oxidisability it is stronger, generated in-situ Ag2O is more, and photoelectric current amplification is bigger, to according to content of nitrogen dioxide and
Up to the present the detection nitrogen dioxide that the linear relationship of photoelectric current amplification can quantify yet there are no two based on the strategy
The report of nitrogen oxide optical electro-chemistry detection method, PhotoelectrochemicalMethod Method detection nitrogen dioxide are still the sky on current technological layer
In vain；With existing detection method such as chromatmetry, semiconductor technology sensor, electrochemical sensor, surface acoustic wave method, gas phase color
The methods of spectrum-mass spectrum combination method, quartz resonance gas sensor mensuration, non-dispersion infrared absorption process there are the shortcomings that phase
Than method of the invention has the characteristics that simple, easy to operate, at low cost, highly selective, highly sensitive.
（2）The present invention is used as the unformed TiO of template controllable preparation by silicon dioxide microsphere2TiO is adulterated with nanometer Ag2It is empty
Bulbus cordis, unformed TiO2Hollow ball is both photoelectricity beacon and the carrier of nanometer silver probe, is gone back in situ using ethanol wash process
Former silver ion（By with unformed TiO2Sodium ion exchange in hollow ball and obtain）Nano silver particles probe is obtained, prepared by this method
Unformed TiO2TiO is adulterated with nanometer Ag2Hollow ball has the advantages that monodisperse and size adjustable；Select unformed TiO2
Hollow ball also has the advantages that acid and alkali-resistance as photoelectricity beacon and nanometer silver probe, can be realized to dioxy within the scope of wider pH
Change the stable detection of nitrogen.
Description of the drawings
Fig. 1（A）For SiO2The field emission scanning electron microscope picture of microballoon, Fig. 1（B）For SiO2 The unformed TiO of@2Flied emission
Scanning electron microscopic picture, Fig. 1（C）For unformed TiO2The high resolution transmission electron microscopy piece of hollow ball, Fig. 1（D）It is received for Ag
Rice corpuscles adulterates unformed TiO2The high resolution transmission electron microscopy piece of hollow ball；Fig. 1（E）、（F）、（G）Respectively Ti, O
With Ag Elemental redistribution pictures.
Fig. 2（a）、（b）、（c）Respectively unformed TiO2, the unformed TiO of Ag nanoparticle dopeds2Hollow ball and Ag2O/Ag
The unformed TiO of nanoparticle doped2The X-ray diffraction spectra figure of hollow ball.
Fig. 3（A）For Ag2The unformed TiO of O/Ag nanoparticle dopeds2Ag 3d x-ray photoelectron spectroscopies, Fig. 3 in hollow ball
（B）For Ag MNN auger electron spectroscopy figures.
Fig. 4（A）In（a）、（b）、（c）Respectively unformed TiO2, the unformed TiO of Ag nanoparticle dopeds2Hollow ball and
Ag2The unformed TiO of O/Ag nanoparticle dopeds2The ultraviolet-visible diffuse reflectance spectrum figure of hollow ball, Fig. 4（B）For unformed TiO2
Valence band spectrogram.
Fig. 5（a）、（b）Respectively unformed TiO2The unformed TiO of/ITO and Ag nanoparticle dopeds2Hollow ball optoelectronic pole exists
Photocurrent curve in 0.1 mol/L PBS (pH 4.0), Fig. 5（c）For the unformed TiO of Ag nanoparticle dopeds2Hollow ball light
Electrode contains 1.0 nmol/L NaNO in 0.1 mol/L PBS (pH 4.0)3Photocurrent curve.
Fig. 6（A）For the unformed TiO of Ag nanoparticle dopeds2Hollow ball optoelectronic pole is in 0.1 mol/L PBS (pH 4.0)
In contain various concentration NaNO3Photocurrent curve, Fig. 6（B）For linear calibration curve.
Fig. 7 is interference block diagram of the common gas to detection architecture.
Specific implementation mode
Technical solution of the present invention is described in detail below by attached drawing, but protection scope of the present invention is not limited to
The embodiment.
Embodiment 1：
（1）Synthesize SiO2Microballoon is as template：Successively by 4.9 mL tetraethyl orthosilicates（99%）, 112 mL absolute ethyl alcohols,
9.0 mL ultra-pure waters, 3.98 mL ammonium hydroxide（26%）It is uniformly mixed successively, and 6 h of reaction is stirred at room temperature；Pass through centrifugation
Obtain SiO2Microballoon is used ethyl alcohol and water washing, is then dispersed in 25 mL ethyl alcohol respectively.
（2）Prepare SiO2@TiO2Microballoon：By the above-mentioned SiO being dispersed in 25 mL ethyl alcohol2Microballoon, 65 mg hydroxy propyl celluloses
Element, 18 mL absolute ethyl alcohols, 12 mL acetonitriles, 0.2 mL ammonium hydroxide are sufficiently mixed 10 min；By the second containing 1 mL butyl titanates
5 mL of alcoholic solution is added into above-mentioned mixed solution, stirs 2 h；By the SiO of generation2@TiO2Microballoon centrifuge washing is collected, and second is used
After alcohol, water wash respectively, it is dispersed in 20 mL water.
（3）TiO2TiO is adulterated with nanometer Ag2The preparation of hollow ball：By 20 mL SiO2@TiO2Microspheres solution is added to 4.2
In a concentration of 2.0 mol/L NaOH solutions of mL, 3.5 h of heating reflux reaction；SiO is etched2After microballoon, TiO is obtained2It is hollow
Ball；After centrifuging, washing, it is dispersed in again in a concentration of 0.1 mmol/L silver nitrate solutions of 10 mL, is persistently stirred
6 h are mixed, after centrifugation, ethyl alcohol washing, in-situ reducing silver ion obtains the nano Ag particles doping TiO of grey2Hollow ball,
Then it is dispersed in 5 mL water.
（4）Nanometer Ag adulterates TiO2Hollow ball modifies ITO electrode：The ITO electrode of the cm of 1 cm × 4 is cleaned up, then will
Above-mentioned steps（3）The nano Ag particles of preparation adulterate TiO2Hollow ball aqueous solution dilutes 30 times, takes its 20 μ L drop coating in ITO electrode
One end, and room temperature be saturated atmosphere in dry；The material that do not modify securely is removed with water rinse, obtains nanometer Ag doping
TiO2Hollow ball modifies ITO electrode.
（5）By above-mentioned steps（4）The nanometer Ag of preparation adulterates TiO2Hollow ball modifies ITO electrode and contains two to various concentration
Nitrogen oxide acidity PBS buffer solution detects；The TiO that nanometer Ag is adulterated according to content of nitrogen dioxide2Hollow ball modifies ITO electrode light
The quantitative effect of electric current establishes quantitative linearity equation and draws quantitation curves.Test condition：Inclined current potential is 0.25 V, 150 W xenons
Light shines.
Before detection, the processing to nitrogen dioxide sample is：It is passed into the NaOH solution of 0.1 mol/L of 10 mL, so
It is adjusted to neutrality afterwards with hydrochloric acid（Convert nitrogen dioxide to equimolar NaNO3）, its 1 mL is then taken to be settled to 30 mL's
PBS（pH 4.0）In.When doing quantitation curves, for convenience, the NaNO of suitable concentration is directly used3Standard specimen solution establishes work
Curve.
According to containing concentration value being respectively 0,1,2,4,6,8,10,20,40,60,80 in 0.1 mol/L PBS buffer solution,
100,200,400,600,800,1000,2000,4000 and 6000 pmol/LNaNO3To step（5）Middle nanometer Ag doping
TiO2Hollow ball modifies the influence of ITO electrode photoelectric current, establishes linear equation.
Detected sample and step（5）The TiO of obtained nanometer Ag doping2Hollow ball modifies ITO electrode effect, is received
Rice Ag2The TiO of O/Ag doping2Hollow ball modifies the photocurrent values of ITO electrode, with step（5）Quantitation curves compare, obtain sample
Nitrogen dioxide content in product.
As shown in Figure 1, pass through SiO2The monodispersed unformed TiO of Ag nanoparticle dopeds of microsphere template method controllable preparation2
Hollow ball.
Due to unformed TiO2Not by calcining, do not crystallize, so from Fig. 2（a）On do not see apparent diffraction maximum；
From Fig. 2（b）Crystal face data can illustrate that nano silver is restored by ethyl alcohol in situ and generate；Compared to Fig. 2（b）, occur
Ag2The 110 and 111 crystal face data of O, other crystal face data unobvious illustrate that the nitrogen dioxide oxidation by low concentration generates
Ag2The amount of O is fewer.
From Fig. 3（A）Going out from the point of view of peak position for the combination energy of middle Ag 3d, further demonstrates the generation of nano-Ag particles；From
Fig. 3（B）From the point of view of the peak ownership of middle Ag MNN auger electron spectroscopies, it was demonstrated that nano silver is partly oxidized to Ag2O；Thus into
Illustrate to one step that method through the invention can detect nitrogen dioxide.
From Fig. 4（A）In（a）It can be seen that unformed TiO2ABSORPTION EDGE is in 340 nm；（b）It can be seen that Ag nano-particles are mixed
Miscellaneous nothing determines TiO2The nano silver of hollow ball has apparent phasmon peak in Liang Chu；Compared to（b）, from（c）It can be seen that Ag2O/
The unformed TiO of Ag nanoparticle dopeds2Ag in hollow ball2The generation of O leads to phasmon peak intensity and position of the nano silver at two
Shifting is changed, and is further demonstrated nano silver and is partially oxidized generation Ag2O.From Fig. 4（B）Unformed TiO2Valence band spectrum on
It can determine that its valence band value is 2.6 eV, to combine the absorption maximum side of its left figure（Eg= 3.65 = 1240/340）It can be with
It is -1.05 eV to extrapolate its conduction band value.The data provide strong proof for its optical electro-chemistry Sensitization Mechanism.
Fig. 6（A）It is the unformed TiO of Ag nanoparticle dopeds2Hollow ball optoelectronic pole is in 0.1 mol/L PBS (pH 4.0)
In contain 0,1,2,4,6,8,10,20,40,60,80,100,200,400,600,800,1000,2000,4000 and 6000
pmol/L NaNO3Photocurrent curve.As can be seen from Figure, the unformed TiO of Ag nanoparticle dopeds2Hollow ball optoelectronic pole exists
Phosphate（PBS）There is the broad linear range of 3 orders of magnitude in buffer solution.
The result shows that the concentration of nitrogen dioxide is bigger, oxidation generates the Ag of black2O is more, and sensitization photoelectric current is more apparent.
To establish novel nitrogen dioxide optical electro-chemistry detection method, this method has excellent selectivity.
Embodiment 2：
（1）Synthesize SiO2Microballoon is as template：Successively by 3.9 mL tetraethyl orthosilicates（99%）, 100 mL absolute ethyl alcohols,
7.0 mL ultra-pure waters, 2.98 mL ammonium hydroxide（26%）It is uniformly mixed successively, and 5 h of reaction is stirred at room temperature；Pass through centrifugation
Obtain SiO2Microballoon is used ethyl alcohol and water washing, is then dispersed in 25 mL ethyl alcohol respectively.
（2）Prepare SiO2@TiO2Microballoon：By the above-mentioned SiO being dispersed in 25 mL ethyl alcohol2Microballoon, 55 mg hydroxy propyl celluloses
Element, 15 mL absolute ethyl alcohols, 10 mL acetonitriles, 0.1 mL ammonium hydroxide are sufficiently mixed 8 min；By the second containing 0.7 mL butyl titanates
3 mL of alcoholic solution is added into above-mentioned mixed solution, stirs 2 h；By the SiO of generation2@TiO2Microballoon centrifuge washing is collected, and second is used
After alcohol, water wash respectively, it is dispersed in 20 mL water.
（3）TiO2TiO is adulterated with nanometer Ag2The preparation of hollow ball：By 20 mL SiO2@TiO2Microballoon is added to 3.2 mL
A concentration of 1.0 mol/L NaOH solutions in, 2.5 h of heating reflux reaction；SiO is etched2After microballoon, TiO is obtained2It is hollow
Ball；After centrifuging, washing, it is dispersed in again in a concentration of 0.05mmol/L silver nitrate solutions of 10 mL, is persistently stirred
6 h are mixed, after centrifugation, ethyl alcohol washing, in-situ reducing silver ion obtains the nano Ag particles doping TiO of grey2Hollow ball,
Then it is dispersed in 5 mL water.
（4）Nanometer Ag adulterates TiO2Hollow ball modifies ITO electrode：The ITO electrode of the cm of 1 cm × 4 is cleaned up, then
By above-mentioned steps（3）The nano Ag particles of preparation adulterate TiO2Hollow ball aqueous solution dilutes 20 times, takes its 20 μ L drop coating in ITO electricity
One end of pole, and be saturated in atmosphere and dry in room temperature；The material that do not modify securely is removed with water rinse, obtains nanometer Ag doping
TiO2Hollow ball modifies ITO electrode.
（5）By above-mentioned steps（4）The nanometer Ag of preparation adulterates TiO2Hollow ball modifies ITO electrode and contains two to various concentration
Nitrogen oxide acidity PBS buffer solution detects；The TiO that nanometer Ag is adulterated according to content of nitrogen dioxide2Hollow ball modifies ITO electrode light
The quantitative effect of electric current establishes quantitative linearity equation and draws quantitation curves.Test condition：Inclined current potential is 0.25 V, 150 W xenons
Light shines.
Specifically, before detection, the processing to nitrogen dioxide sample is：The NaOH for being passed into 0.1 mol/L of 10 mL is molten
In liquid, then it is adjusted to neutrality with hydrochloric acid（Convert nitrogen dioxide to equimolar NaNO3）, its 1 mL is then taken to be settled to 30
The PBS of mL（pH 3.0）In.When doing quantitation curves, for convenience, the NaNO of suitable concentration is directly used3Standard specimen solution is built
Vertical working curve.
According to containing concentration value being respectively 0,1,2,4,6,8,10,20,40,60,80 in 0.1 mol/L PBS buffer solution,
100,200,400,600,800,1000,2000,4000 and 6000 pmol/LNaNO3To step（5）Middle nanometer Ag doping
TiO2Hollow ball modifies the influence of ITO electrode photoelectric current, establishes linear equation.
Detected sample and step（5）The TiO of obtained nanometer Ag doping2Hollow ball modifies ITO electrode effect, is received
Rice Ag2The TiO of O/Ag doping2Hollow ball modifies the photocurrent values of ITO electrode, with step（5）Quantitation curves compare, obtain sample
Nitrogen dioxide content in product.
Embodiment 3：
（1）Synthesize SiO2Microballoon is as template：Successively by 5.9 mL tetraethyl orthosilicates（99%）, 125 mL absolute ethyl alcohols,
11.0 mL ultra-pure waters, 4.38 mL ammonium hydroxide（26%）It is uniformly mixed successively, and 7 h of reaction is stirred at room temperature；Pass through centrifugation
Obtain SiO2Microballoon is used ethyl alcohol and water washing, is then dispersed in 25 mL ethyl alcohol respectively.
（2）Prepare SiO2@TiO2Microballoon：By the above-mentioned SiO being dispersed in 25 mL ethyl alcohol2Microballoon, 75 mg hydroxy propyl celluloses
Element, 20 mL absolute ethyl alcohols, 14 mL acetonitriles, 0.3 mL ammonium hydroxide are sufficiently mixed 10 min；1.2 mL butyl titanates will be contained
9 mL of ethanol solution is added into above-mentioned mixed solution, stirs 2.5 h；By the SiO of generation2@TiO2Microballoon centrifuge washing is collected,
After being washed respectively with ethyl alcohol, water, it is dispersed in 20 mL water.
（3）TiO2TiO is adulterated with nanometer Ag2The preparation of hollow ball：By 20 mL SiO2@TiO2Microballoon is added to 4.2 mL
A concentration of 2.5 mol/L NaOH solutions in, 4.5 h of heating reflux reaction；SiO is etched2After microballoon, TiO is obtained2It is hollow
Ball；After centrifuging, washing, it is dispersed in again in a concentration of 0.2 mmol/L silver nitrate solutions of 10 mL, is continued
6 h are stirred, after centrifugation, ethyl alcohol washing, in-situ reducing silver ion obtains the nano Ag particles doping TiO of grey2It is hollow
Then ball is dispersed in 5 mL water.
（4）Nanometer Ag adulterates TiO2Hollow ball modifies ITO electrode：The ITO electrode of the cm of 1 cm × 4 is cleaned up, then
By above-mentioned steps（3）The nano Ag particles of preparation adulterate TiO2Hollow ball aqueous solution dilutes 30 times, takes its 20 μ L drop coating in ITO electricity
One end of pole, and be saturated in atmosphere and dry in room temperature；The material that do not modify securely is removed with water rinse, obtains nanometer Ag doping
TiO2Hollow ball modifies ITO electrode；TiO for comparison2Hollow ball modifies ITO electrode and is similar to the above method, only without
Nanometer Ag doping.
（5）By above-mentioned steps（4）The nanometer Ag of preparation adulterates TiO2Hollow ball modifies ITO electrode and contains two to various concentration
Nitrogen oxide acidity PBS（pH=4）Buffer solution detects；The TiO that nanometer Ag is adulterated according to content of nitrogen dioxide2Hollow ball modifies ITO
The quantitative effect of electrode photoelectric stream establishes quantitative linearity equation and draws quantitation curves.Test condition：Inclined current potential is 0.25 V,
150 W Xenon light shinings.
Specifically, before detection, the processing to nitrogen dioxide sample is：The NaOH for being passed into 0.1 mol/L of 10 mL is molten
In liquid, then it is adjusted to neutrality with hydrochloric acid（Convert nitrogen dioxide to equimolar NaNO3）, its 1 mL is then taken to be settled to 30
The PBS of mL（pH 4.0）In.When doing quantitation curves, for convenience, the NaNO of suitable concentration is directly used3Standard specimen solution is built
Vertical working curve.According to containing concentration value being respectively 0,1,2,4,6,8,10,20,40,60 in 0.1 mol/L PBS buffer solution,
80,100,200,400,600,800,1000,2000,4000 and 6000 pmol/LNaNO3To step（5）Middle nanometer Ag doping
TiO2Hollow ball modifies the influence of ITO electrode photoelectric current, establishes linear equation.
Detected sample and step（5）The TiO of obtained nanometer Ag doping2Hollow ball modifies ITO electrode effect, is received
Rice Ag2The TiO of O/Ag doping2Hollow ball modifies the photocurrent values of ITO electrode, with step（5）Quantitation curves compare, obtain sample
Nitrogen dioxide content in product.
Comparative example 1：In the comparative example, when modifying working electrode, while two groups of control experiments are established, first group with TiO2
Nano-hollow ball modifies ITO electrode, and second group with Ag nanoparticle dopeds TiO2Hollow ball modifies ITO electrode.Remaining the step of
It is consistent with each embodiment.Wherein, the TiO that Ag is adulterated in first group of electrode and 3 embodiments2Nano-hollow ball modifies ITO electricity
The test condition of pole is identical：In the 0.1 mol/L PBS of pH 4.0, inclined current potential be 0.25 V, incident light source is 150 W
Xenon light shining；The test condition of second group of electrode is：Contain 1.0 nmol/ in the 0.1 mol/L PBS of pH 4.0
LNaNO3, inclined current potential be 0.25 V, the Xenon light shining that incident light source is 150 W.Test results are shown in figure 5 for each group.
A, b are unformed TiO respectively in Fig. 52The unformed TiO of/ITO and Ag nanoparticle dopeds2Hollow ball optoelectronic pole exists
Photocurrent curve in 0.1 mol/L PBS (pH 4.0)；C is the unformed TiO of Ag nanoparticle dopeds2Hollow ball optoelectronic pole
Containing 1.0 nmol/L NaNO3 0.1 mol/L PBS (pH 4.0) in photocurrent curve.Compared to photocurrent curve
A, Ag nano-particle, which absorb visible light, can be sensitized photoelectric current b；Compared to photocurrent curve b, generated in-situ Ag2O can be into
The light absorption of one step enhancing Ag nano-particles simultaneously improves its photoelectric current c；Nitrogen dioxide optical electro-chemistry is constructed according to this principle
New detecting method.
Comparative example 2：In the comparative example, in order to verify the feasibility of the test method, with 10 times of NH4 +, 5 times of SO4 2-、5
HSO again3 -, 10 times of S2-, 50 times of HCO3 -, 50 times of Cl- This detection architecture is added in each above-mentioned Ar ion mixing with 5 times
In.The result shows that, above-mentioned this detection architecture of ion pair does not constitute interference in Fig. 7, and this method has excellent selectivity.
As described above, although the present invention has been indicated and described with reference to specific preferred embodiment, must not explain
For the limitation to invention itself.It without prejudice to the spirit and scope of the invention as defined in the appended claims, can be right
Various changes can be made in the form and details for it.
Claims (7)
1. a kind of PhotoelectrochemicalMethod Method of highly sensitive detection nitrogen dioxide, it is characterised in that include the following steps：
（1）Synthesize SiO2Microballoon is as template：Successively by the tetraethyl orthosilicate of 3.9 ~ 5.9 mL 99%, 100 ~ 125 mL without
Water-ethanol, 7.0 ~ 11.0 mL ultra-pure waters, 2.98 ~ 4.38 mL, 26% ammonium hydroxide are uniformly mixed, and reaction 5 are stirred at room temperature successively
~7 h；By being centrifugally separating to obtain SiO2Microballoon is used ethyl alcohol and water washing, is then dispersed in ethyl alcohol respectively；
（2）Prepare SiO2@TiO2Microballoon：By the SiO of above-mentioned dispersion in ethanol2Microballoon, 55 ~ 75 mg hydroxypropyl celluloses, 15 ~
20 mL absolute ethyl alcohols, 10 ~ 14 mL acetonitriles and 0.1 ~ 0.3 mL ammonium hydroxide are sufficiently mixed 8 ~ 10 min；0.7 ~ 1.2 mL titaniums will be contained
3 ~ 9 mL of ethanol solution of sour four butyl esters is added into above-mentioned mixed solution, stirs at least 1 h；By the SiO of generation2@TiO2Microballoon
Centrifuge washing is collected, and after being washed respectively with ethyl alcohol, water, is dispersed in water；
（3）TiO2TiO is adulterated with nanometer Ag2The preparation of hollow ball：By SiO2@TiO2Microballoon is added molten to 3.2 ~ 4.2 mL NaOH
In liquid, 2.5 ~ 4.5 h of heating reflux reaction has etched SiO2After microballoon, TiO is obtained2Hollow ball；After centrifuging, washing,
The TiO that will be obtained2Hollow ball is dispersed in silver nitrate solution again, continues stirring until few 5h, it is washed by centrifugation, ethyl alcohol
Afterwards, in-situ reducing silver ion obtains nano Ag particles doping TiO2Then hollow ball is dispersed in water；
（4）Nanometer Ag adulterates TiO2Hollow ball modifies ITO electrode：After ITO electrode is cleaned up, by step（3）The nanometer of preparation
Ag particles adulterate TiO2Drop coating is in one end of ITO electrode after hollow ball aqueous solution dilutes 20 ~ 30 times, and under room temperature saturated environment
It dries；With water rinse, nanometer Ag doping TiO is obtained2Hollow ball modifies ITO electrode；
（5）By above-mentioned steps（4）The nanometer Ag of preparation adulterates TiO2Hollow ball modifies ITO electrode to containing various concentration titanium dioxide
The acid PBS buffer solution of nitrogen detects；The TiO that nanometer Ag is adulterated according to content of nitrogen dioxide2Hollow ball modifies ITO electrode photoelectricity
The quantitative effect of stream establishes quantitative linearity equation and draws quantitation curves.
2. the PhotoelectrochemicalMethod Method of highly sensitive detection nitrogen dioxide according to claim 1, which is characterized in that step（5）
The preparation method of the acid PBS buffer solution of middle nitrogen dioxide is：Nitrogen dioxide is passed through in NaOH solution, is then adjusted with hydrochloric acid
Then the solution is settled in acid PBS buffer solution by solution to neutrality；Nitrogen dioxide is converted into equimolar NaNO3,
When doing quantitation curves, the NaNO of suitable concentration is directly used3Standard specimen solution establishes working curve.
3. the PhotoelectrochemicalMethod Method of highly sensitive detection nitrogen dioxide according to claim 2, which is characterized in that according to PBS
Containing concentration value it is respectively 0,1,2,4,6,8,10,20,40,60,80,100,200,400,600,800,1000 in buffer solution,
The NaNO of 2000,4000 and 6000 pmol/L3To step（5）The TiO of middle nanometer Ag doping2Hollow ball modifies ITO electrode photoelectricity
The influence of stream, establishes linear equation.
4. the PhotoelectrochemicalMethod Method of highly sensitive detection nitrogen dioxide according to claim 1, which is characterized in that step（3）
Described in NaOH solution a concentration of 1.0 ~ 2.5 mol/L.
5. the PhotoelectrochemicalMethod Method of highly sensitive detection nitrogen dioxide according to claim 1, which is characterized in that step（3）
Described in silver nitrate solution a concentration of 0.05 ~ 0.2 mmol/L.
6. the PhotoelectrochemicalMethod Method of highly sensitive detection nitrogen dioxide according to claim 1, which is characterized in that step（4）
Described in nano Ag particles adulterate TiO2Hollow ball aqueous solution extension rate is 30 times.
7. the PhotoelectrochemicalMethod Method of highly sensitive detection nitrogen dioxide according to claim 1, which is characterized in that step（5）
Described in acidity PBS pH be 3.0 ~ 4.0.
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