CN103913448B - Real-time dynamic detection system for hydroxyl radicals generated by photo-catalytic reaction - Google Patents
Real-time dynamic detection system for hydroxyl radicals generated by photo-catalytic reaction Download PDFInfo
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Abstract
The invention discloses a real-time dynamic detection system for hydroxyl radicals generated by photo-catalytic reaction. The real-time dynamic detection system comprises an excitation light source, a photo-catalyst and hydroxyl capturing probe storing container, at least one oxidant storing container, a detection pond, a photomultiplier and a signal analyzer host, wherein both the photo-catalyst and hydroxyl capturing probe storing container and the oxidant storing container are communicated with the detection pond; the photomultiplier is used for converting optical signals generated in the detection pond to electric signals; the photomultiplier is connected with the signal analyzer host; the signal analyzer host is connected with a computer terminal. A method for detecting by using the real-time dynamic detection system is simple to operate; the processes of separating samples offline and then detecting the sample online and the like are omitted, and therefore, the method is high in detection speed, capable of improving the working efficiency and applicable to quick screening and evaluation of hydroxyl-generating capability of a photo-catalytic material.
Description
Technical field
The present invention relates to a kind of light-catalyzed reaction produces the Real-time and Dynamic Detection system of hydroxyl radical free radical.
Background technology
Hydroxyl radical free radical (oh) has very strong oxidability (e=2.7 or 1.8v is under acidic or neutral conditions), several
Can degrade all of organic pollution, therefore cause people's greatly research enthusiasm.In natural environment, oh is main
Come from light Fenton's reaction, photodissociation of nitrate and natural organic matter (nom) etc..In engineering field, particularly in recent years not
In the high-level oxidation technology of disconnected development (aot), such as Fenton's reaction, ozone oxidation, electrolytic oxidation etc., oh is topmost one kind
Active substance, has played conclusive effect wherein, has therefore also obtained extensive concern and in-depth study.At present, light is urged
Change technology, as a kind of new high-level oxidation technology, is greatly ground due to causing people the advantages of its green, energy-saving and environmental protection
Study carefully enthusiasm.The main operational principle of conductor photocatalysis is (with tio2As a example): work as tio2It is equal to or more than it by energy
After the photon excitation of gap width, the valence-band electrons positioned at ground state are excited to conduction band, thus generate valence band oxidation hole and
The free electron (electron-hole pair) of conduction band.Electron-hole pair has strong reduction and oxidability, and can freely move
Move, with the small molecule of surface adsorption (as h after they move to semiconductor surface2o、oh-、o2) there is a series of reaction life
Viability oxygen class species (mainly oh, o2 ·-、h2o2).Wherein oh is a kind of very important work in light-catalyzed reaction
Property oxygen, it play during photocatalytic oxidation degradation pollutant key effect.Additionally, oh can destroy the thin of microorganism
Cell wall, also plays an important role during the photo-catalyst of catalysis material.Therefore, the generation quantity of oh is to weigh
A kind of important indicator of properties of catalyst.But the property of oh is active, short life (delicate level), and it is measured is one
The huge challenge of item.
The method of the measurement oh commonly using at present mainly has electronic self-rotary resonant technology (esr) and fluorescence probe method, but
These methods in actual applications, particularly in photocatalysis field, have its respective limitation.For example, current esr is the most frequently used
Capture probe be dmpo, but its capture specificity aspect still have dispute.Catalysis material can produce in light-catalyzed reaction
Raw oxidation hole, has scholar's research to think, the adduct that dmpo reacts generation with oxidation hole is identical with the adduct of oh, this
May result in the too high ability estimating that catalysis material produces oh.Fluorescence method is also the common method measuring oh at present,
Developed many probe molecules planted and measure for oh, but the specificity of some probe molecules also exists at present to be striven
View.In addition, when measuring the oh that light-catalyzed reaction produces, their general operating processes are first probe to be added to body to be measured
In system, take out a part after reaction and carry out separating, machine of then going up again measures, therefore complex operation step is unfavorable for oh's
Rapid and accurate determination.Therefore, a kind of simple, quick, accurate, special method measuring oh in light-catalyzed reaction of exploitation has
Significance.
Content of the invention
It is an object of the invention to provide a kind of light-catalyzed reaction produces the Real-time and Dynamic Detection system of hydroxyl radical free radical, this
Bright flowing chemical photic device is combined it is achieved that simple to the oh producing in light-catalyzed reaction, soon with photocatalysis apparatus
Fast, real-time, online, sensitive, special mensure, is used as the assessment that light-catalyzed reaction produces oh ability, and by surveying
Determine the generative capacity of oh, evaluate other performance (such as the photocatalytic oxidation degradation ability and killing of relative catalysis material
Bacterium ability), and the generation behavioral study of catalysis material generation oh.
Light-catalyzed reaction provided by the present invention produces the Real-time and Dynamic Detection system of hydroxyl radical free radical, including exciting light
Source, photocatalyst and hydroxyl capture probe container, at least one oxidant container, detection cell, photomultiplier tube and
Signal analyzer main frame；
Described photocatalyst and hydroxyl capture probe container and described oxidant container all with described detection cell
It is connected；
Described photomultiplier tube is used for for the optical signal producing in described detection cell being converted into the signal of telecommunication；
Described photomultiplier tube is connected with described signal analyzer main frame, and described signal analyzer main frame and a computer are eventually
End is connected.
In above-mentioned Real-time and Dynamic Detection system, described photocatalyst and hydroxyl capture probe container and described detection
It is provided with peristaltic pump between pond, pump into photocatalyst and capture probe with quantitative in described detection cell；
It is provided with peristaltic pump, with quantitative to pump in described detection cell between described oxidant container and described detection cell
Enter oxidant.
In above-mentioned Real-time and Dynamic Detection system, described excitation source be ultraviolet lamp source (as mercury lamp) or visible light source (such as
Xenon lamp).
The oh that Real-time and Dynamic Detection system of the present invention can produce in on-line determination light-catalyzed reaction, it is possible to achieve right
Oh generates the continuous track determining of real-time online of behavior, the dynamic information changing by luminous signal, studies light-catalyzed reaction
Generate the generation behavior of oh, the evaluation further realizing the performance related to oh to catalysis material is (as photocatalytic-oxidation
Change degradation of contaminant ability and sterilizing ability).
Real-time and Dynamic Detection system of the present invention specifically can measure photocatalyst such as titanium dioxide or zinc oxide etc. and produce
The ability of oh；Selected capture probe is phthalylhydrazine (phth)；2 described oxidant containers are set simultaneously,
Hold h respectively2o2And k5cu(hio6)2.
The present invention compared with prior art, has the advantage that
1) Real-time and Dynamic Detection system instrument device of the present invention is simple, and low cost is it is easy to business promotion.
2) use the sensitivity height of Real-time and Dynamic Detection system detectio of the present invention, specificity is good, by catching to oh original position
Obtain, the adduct stable in properties of generation, overcome the problem of its short life.
3) using Real-time and Dynamic Detection system detectio of the present invention method simple to operate it is not necessary to be divided offline to sample
From then going up the processes such as machine testing, therefore finding speed is fast, improve work efficiency it is adaptable to generate to catalysis material
The rapid screening of oh ability and assessment.
4) when using Real-time and Dynamic Detection system detectio of the present invention, online the real time measure, can be generated with online tracing oh
Dynamic change, by dynamic information, study its generation behavior.
Brief description
Fig. 1 (a) light-catalyzed reaction of the present invention produces the schematic diagram of the Real-time and Dynamic Detection system of hydroxyl radical free radical.
Fig. 1 (b) is the schematic diagram after setting up six-way valve in Real-time and Dynamic Detection system shown in Fig. 1 (a).
In Fig. 1 (a) and Fig. 1 (b), each labelling is as follows:
1 excitation source, 2 photocatalysts and hydroxyl capture probe container, 3,4 oxidant containers, 5 detection cells, 6
Photomultiplier tube, 7 signal analyzer main frames, 8 computer terminals, 9,10,11,12 peristaltic pumps, 13 carrier fluid containers, 14 clematis stem
Valve.
Fig. 2 mix with two kinds of oxidants with colloidal tio 2 for hydroxyl capture probe after chemiluminescence signal in time
Change, wherein Fig. 2 (a) be light excite before and after's titanium dioxide (p25) colloid continuously flow with oxidant mix after chemiluminescence believe
Number over time；Fig. 2 (b) excites before and after's titanium dioxide (p25) colloid chemical after mixing with oxidant flow injection for light
Luminous signal is over time；P25(0.1mg/ml), phth(1 μm), h2o2(50 μm), k5cu(hio6)2(100 μm), light intensity
(0.8mw/cm2).
Fig. 3 is to add after different quenchers chemiluminescence signal compared with matched group to capture probe and titania solution
Over time, wherein, Fig. 3 (a) is to add chemiluminescence compared with matched group after hydroxyl radical free radical quencher (isopropanol)
Signal is over time；Fig. 3 (b) is to add after superoxide radical quencher (sod) chemiluminescence signal compared with matched group
Over time；Fig. 3 (c) is to add singlet oxygen quencher (nan3) after chemiluminescence signal is in time compared with matched group
Change；Isopropanol (0.1m), sod(6u/ml), nan3(1 μm).
Specific embodiment
Experimental technique used in following embodiments if no special instructions, is conventional method.
Material used, reagent etc. in following embodiments, if no special instructions, all commercially obtain.
The Real-time and Dynamic Detection system of hydroxyl radical free radical as shown in Fig. 1 (a), is produced for the light-catalyzed reaction that the present invention provides
Including excitation source 1, photocatalyst and 2,2 oxidant containers 3 of hydroxyl capture probe container and 4, detection cell 5 and
Photomultiplier tube 6.Excitation source 1 may be selected mercury lamp or xenon lamp, is used for exciting photocatalyst.Photocatalyst and hydroxyl capture probe
Container 2 is used for holding photocatalyst to be detected and capture probe phth, photocatalyst and capture probe container 2 with
Detection cell 5 is connected, and is provided with a peristaltic pump 9 between them, for providing power.Oxidant container 3 and 4 is used for containing
Put oxidant, the product (5- hydroxyl-phthalylhydrazine) after the hydroxyl radical free radical being produced with photocatalyst is combined with probe is sent out
Biochemical luminescence-producing reaction, produces luminous signal, to be detected, oxidant container 3 is connected with detection cell 5 with 4, and it
Between be provided with a peristaltic pump 10,11, for providing power.Photomultiplier tube 6 is used for the optical signal that will produce in detection cell 5
Change into the signal of telecommunication, be then transmit to signal analyzer main frame 7, signal analyzer main frame 7 is connected with computer terminal 8, will examine
Survey result to be shown.
, the tool of the present embodiment Real-time and Dynamic Detection system is described taking titanium dioxide semiconductor catalysis material (p25) as a example
Body implementation process:
As shown in Fig. 1 (a), first a certain amount of phth is added to equipped with the container 2 of colloidal tio 2, when
Experiment is when carrying out, start flow device by colloidal tio 2 be sent in sensing chamber with other two kinds of oxidant (h2o2And k5cu
(hio6)2) mixing generation chemiluminescence reaction, produce luminous signal, the photomultiplier tube 6 being simultaneously located at below detection cell will connect
The optical signal receiving is converted into the signal of telecommunication, after processing and amplifying, by data line transfer to computer display screen.When light source not
During unlatching, due to not having the generation of oh in colloidal tio 2, phth in colloid is very low due to luminous efficiency, when in detection
After mixing with oxidant in pond, luminous signal is very faint, and very low in time continuous background occurs in computer display screen
Signal (Fig. 2 (a))；Conversely, when light source is opened, titanium dioxide can produce oh after being excited, now the phth in solution
It can be carried out with specific capture, generate 5-oh-phth, 5-oh-phth has high photoluminescence quantum yield, when in detection cell
In mix with oxidant after can produce strong chemiluminescence signal, and persistently carry out with illumination, oh is constantly captured,
The therefore amount of 5-oh-phth is constantly accumulated in the solution, and the luminous signal of generation constantly strengthens, and therefore occurs in display screen
One continuous enhanced chemiluminescence signal curve in time, after the phth in solution is totally consumed, now chemiluminescence
Intensity reaches platform (Fig. 2 (a)).
As shown in Fig. 1 (b), it is with the difference of Fig. 1 (a), in photocatalyst and capture probe container 2 and oxygen
Reconnect a six-way valve 14 between agent container 3 and 4 and detection cell 5, equally first phth is added to titanium dioxide glue
In body, when experiment starts, start flow device and adjust six-way valve by colloidal tio 2 by from carrier fluid container 13
Carrier fluid is sent in detection cell and is mixed with oxidant, and when light source is not opened, colloidal tio 2 passes through six-way valve 14 and enters inspection
Survey pond 5, now due to not having oh to produce, do not have 5-oh-phth to generate in solution, therefore there is no obvious peak shape signal；When
When light source is opened, colloidal tio 2 produces oh, generates 5-oh-phth, therefore work as colloidal tio 2 after being captured by phth
Mix generation chemiluminescence reaction with oxidant after six-way valve 14 enters sensing chamber, produce luminous signal.Due to injection
There is diffusion process in pipeline transport process in titanium dioxide colloid solution, lead to 5-oh-phth concentration from center to both sides by
Decrescence little, an obvious peak shape signal therefore can be produced on display screen, and peak intensity as well as the time prolongation and not
Disconnected strengthen, finally reach platform (Fig. 2 (b)), show that the phth in now colloid is totally consumed.
In order to verify the above-mentioned luminous signal detecting further from oh, the present invention is to this Real-time and Dynamic Detection system
Specificity during detection is investigated.
As shown in figure 3, adding different quenchers that active oxygen is carried out with specificity capture in colloidal tio 2, experiment is sent out
Existing o2 ·-With1o2Quencher sod and nan3On chemiluminescence intensity all no impacts it was demonstrated that o2 ·-With1o2Minimizing to 5-oh-phth
Generation do not affect；And hydroxyl radical free radical quencher can completely inhibit chemiluminescent enhancing it was demonstrated that oh is quenched agent
It is suppressed that the generation of 5-oh-phth after competition capture.Therefore, can be specific using Real-time and Dynamic Detection system of the present invention
Detection oh.
Claims (4)
1. a kind of Real-time and Dynamic Detection system of light-catalyzed reaction generation hydroxyl radical free radical is evaluating photocatalyst generation hydroxyl certainly
By the application in the ability of base it is characterised in that: described Real-time and Dynamic Detection system includes excitation source, photocatalyst and hydroxyl
Capture probe container, at least one oxidant container, detection cell, photomultiplier tube and signal analyzer main frame；
Described photocatalyst is all connected with described detection cell with described oxidant container with hydroxyl capture probe container
Logical；
Described photomultiplier tube is used for for the optical signal producing in described detection cell being converted into the signal of telecommunication；
Described photomultiplier tube is connected with signal analyzer main frame, and described signal analyzer main frame is connected with a computer terminal
Connect；
It is provided with peristaltic pump between described photocatalyst and hydroxyl capture probe container and described detection cell；
It is provided with peristaltic pump between described oxidant container and described detection cell；
The hydroxyl capture probe holding in described photocatalyst and hydroxyl capture probe container is phthalylhydrazine.
2. according to claim 1 application it is characterised in that: described excitation source be ultraviolet lamp source or visible light source.
3. according to claim 1 application it is characterised in that: described photocatalyst be titanium dioxide or zinc oxide.
4. according to claim 1 application it is characterised in that: described Real-time and Dynamic Detection system includes 2 described oxidations
Agent container, holds h respectively2o2And k5cu(hio6)2.
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| CN105136972A (en) * | 2015-09-09 | 2015-12-09 | 武汉理工大学 | Comparison detection method for nano photocatalytic activity capability |
| CN108169218A (en) * | 2017-12-15 | 2018-06-15 | 中国科学院合肥物质科学研究院 | A kind of hydroxy radical in-situ measurement system |
| CN110554026B (en) * | 2018-05-30 | 2021-11-09 | 中国农业科学院烟草研究所 | Chemiluminescence method for detecting hydroxyl free radicals |
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| CN103033485A (en) * | 2011-09-29 | 2013-04-10 | 中科天融(北京)科技有限公司 | Water total-phosphorus and total-nitrogen online monitoring apparatus |
| CN103616525A (en) * | 2013-12-11 | 2014-03-05 | 三峡大学 | Instrument for rapidly monitoring total phosphorus in water on line |
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| CN101929975B (en) * | 2010-07-30 | 2013-06-05 | 同济大学 | Electrochemical analysis method for hydroxyl radicals |
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| CN103033485A (en) * | 2011-09-29 | 2013-04-10 | 中科天融(北京)科技有限公司 | Water total-phosphorus and total-nitrogen online monitoring apparatus |
| CN103616525A (en) * | 2013-12-11 | 2014-03-05 | 三峡大学 | Instrument for rapidly monitoring total phosphorus in water on line |
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