CN106645339A - Thin-layer flow type photoelectric detector and oxidation resisting capacity detection method - Google Patents
Thin-layer flow type photoelectric detector and oxidation resisting capacity detection method Download PDFInfo
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- CN106645339A CN106645339A CN201611232899.5A CN201611232899A CN106645339A CN 106645339 A CN106645339 A CN 106645339A CN 201611232899 A CN201611232899 A CN 201611232899A CN 106645339 A CN106645339 A CN 106645339A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/301—Reference electrodes
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/32—Calomel electrodes
Abstract
The invention provides a thin-layer flow type photoelectric detector. The thin-layer flow type photoelectric detector comprises a sample pool, wherein the sample pool is provided with a sample solution inlet and a sample solution outlet; a transparent working electrode is arranged at the bottom of the sample pool; an LED (Light Emitting Diode) light source is arranged below the working electrode; a counter electrode and a reference electrode are arranged in the sample pool; the surface of the working electrode is coated with one or more of a carbon nitrogen/titanium dioxide composite nano-material, a carbon nitrogen/zinc oxide composite nano-material, a carbon powder/titanium dioxide composite nano-material, a graphene/titanium dioxide composite nano-material and a graphene/zinc oxide composite nano-material. Compared with the prior art, the photoelectric detector provided by the invention has the advantages that the operation is simple and convenient, the cost is low, and an incidence mode of the light source is a back incidence mode, so that the influence caused by background signals of colored samples can be avoided to the maximum. In addition, with thin-layer flow type sample introduction, the condition that detected photocurrent remains constant is facilitated, the capability of mass transfer is improved, and the sensitivity is improved greatly.
Description
Technical field
The invention belongs to optoelectronic materials technology, more particularly to Thin Film Flows dynamic formula photoelectric detector and antioxidant capacity
Detection method.
Background technology
With the development and the improvement of people's living standards of national economy, disease and aging become what everybody increasingly paid close attention to
Topic.Since Denham Harman teach the aging free-radical theory proposed in 1956, researchers are to polyphenoils
Quality Research interest is lasting.Antioxidant needed by human is suitably supplemented in time to promoting health by food, is subtracted
Few disease occurs have positive effect.By food supplement antioxidant mainly include vitamin E, vitamin C, carrotene,
The material such as flavonoids and polyphenol.A series of cells and histological examination have confirmed that the antioxidant in these food can be to oxygen
Change damage to play a protective role.Therefore, the measure of antioxidant and oxidation resistance is had great importance.
Being usually used in the method for antioxidant detection at present has three kinds：Spectroscopic methodology；Chromatography and electrochemical method.However, three
In addition to kind of method is the shortcomings of cumbersome, expensive equipment, in each comfortable anti-oxidant detection the inferior position of itself is shown.Spectroscopic methodology
When determining, easy tested person color sample interference, makes determination data serious distortion when serious；Although chromatography can be determined accurately
The concentration of every kind of antioxidant, but concentration and oxidation resistance have significant difference, while the cooperative effect between antioxidant is not
Can be determined；Working electrode is easily poisoned in electrochemical method, poor reproducibility.Therefore it is badly in need of a kind of new method solution above-mentioned
Problem.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of Thin Film Flows dynamic formula photoelectric detector and antioxygen
Change the detection method of capacity, the reappearance of the detection method is preferable.
The invention provides a kind of Thin Film Flows dynamic formula photoelectric detector, including：Sample cell, the sample cell is provided with sample
Solution inlet port is exported with sample solution；The bottom of the sample cell is transparent working electrode；Set below the working electrode
It is equipped with LED/light source；It is provided with the sample cell to electrode and reference electrode；The surface of the working electrode be coated with carbon nitrogen/
Titanium dioxide composite nano material, carbon nitrogen/zinc oxide compound nano material, carbon dust/titanium dioxide composite nano material, graphite
One or more in alkene/titanium dioxide composite nano material and Graphene/zinc oxide compound nano material.
Preferably, the area of the working electrode is 1～200mm2；The area to electrode is 1～80mm2。
Preferably, described is platinum filament, platinized platinum, titanium sheet or carbon plate to electrode；The reference electrode is that Ag/AgCl or saturation are sweet
Mercury electrode.
Preferably, the carbon nitrogen/composite titania material is prepared in accordance with the following methods：
Melamine is calcined in protective atmosphere high temperature, ultrasonic disperse obtains carbonitride in water；
Carbonitride, trivalent titanium salt, hydrogen peroxide are mixed with anion surfactant in water, heating response, in obtaining
Between product；
The intermediate product is calcined in protective atmosphere, carbon nitrogen/composite titania material is obtained.
Preferably, the ratio of titanium ion is 1g in the carbonitride and trivalent titanium salt：(2～4) mol；The carbonitride with
The mass ratio of anion surfactant is 3：(1.5～2.5).
Preferably, the temperature of the heating response is 80 DEG C～100 DEG C；The time of the heating response is 10～30h；Institute
The temperature for stating calcining is 400 DEG C～500 DEG C；The time of the calcining is 1～4h.
Present invention also offers a kind of detection method of antioxidant capacity, comprises the following steps：
Using above-mentioned Thin Film Flows dynamic formula photoelectric detector；
Testing sample solution is injected in sample cell by sample solution import, the detection of antioxidant capacity is carried out.
Preferably, the operating voltage of the working electrode is -0.2～0.4V.
Preferably, the injection flow velocity of the testing sample solution is 0.1～50ml/min.
Preferably, the wavelength of the LED/light source is 380～560nm.
The invention provides a kind of Thin Film Flows dynamic formula photoelectric detector, including：Sample cell, the sample cell is provided with sample
Solution inlet port is exported with sample solution；The bottom of the sample cell is have transparent working electrode；The lower section of the working electrode
It is provided with LED/light source；It is provided with the sample cell to electrode and reference electrode；The surface of the working electrode is coated with carbon
Nitrogen/titanium dioxide composite nano material, carbon nitrogen/zinc oxide compound nano material, carbon dust/titanium dioxide composite nano material, stone
One or more in black alkene/titanium dioxide composite nano material and Graphene/zinc oxide compound nano material.With prior art
Compare, the photoelectric detector that the present invention is provided is easy to operate, with low cost, can promptly carry out the inspection of antioxidant antioxidant capacity
Survey；The incidence of its light source is back reflection type, can maximize the impact for avoiding colored samples background signal.In addition Thin Film Flows dynamic formula
The introducing of sample introduction, not only contributes to measure photoelectric current and keeps constant, and improves mass transfer ability, and sensitivity is greatly promoted.
Description of the drawings
Fig. 1 is the dispersion liquid picture of the carbonitride with ultra-thin carbonitride of the body obtained in the embodiment of the present invention 1；
Fig. 2 is the atomic force microscopy of the ultra-thin carbonitride obtained in the embodiment of the present invention 1；
Fig. 3 is the force curve of atomic force microscope figure of the ultra-thin carbonitride obtained in the embodiment of the present invention 1；
Fig. 4 is the transmission electron microscope photo of the ultra-thin carbonitride obtained in the embodiment of the present invention 1；
Fig. 5 is the transmission electron microscope photo of the carbonitride of the body obtained in the embodiment of the present invention 1；
Fig. 6 is the transmission electron microscope photo of the carbon nitrogen/titanium dioxide composite nano material obtained in the embodiment of the present invention 1；
Fig. 7 is that the high-resolution-ration transmission electric-lens of the carbon nitrogen/titanium dioxide composite nano material obtained in the embodiment of the present invention 1 shine
Piece；
Fig. 8 is that carbonitride, ultra-thin carbonitride and the carbon nitrogen/titanium dioxide of the body obtained in the embodiment of the present invention 1 are multiple
Close the X-ray diffraction spectrogram of nano material；
Fig. 9 a are the X-ray of the ultra-thin carbonitride and carbon nitrogen/composite titania material obtained in the embodiment of the present invention 1
Photoelectron spectroscopy figure；；Fig. 9 b-d are each element in the ultra-thin carbon nitrogen/composite titania material obtained in the embodiment of the present invention 1
X-ray photoelectron energy spectrum diagram；
Figure 10 is the TiO obtained in the embodiment of the present invention 12(a0, a1), bg-C3N4/TiO2(b0, b1) and utg-C3N4/
TiO2The photoelectric respone signal graph of (c0, c1) three kinds of materials；
The structural representation of the Thin Film Flows dynamic formula photoelectric detector that Figure 11 is provided for the present invention；
Figure 12 is the anti-interference test result figure of gallic acid antioxidant capacity in the embodiment of the present invention 2；
Figure 13 is the photoelectric respone figure of tri- kinds of antioxidants of CA, CT and AA under variable concentrations in the embodiment of the present invention 3.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the invention, rather than the embodiment of whole.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, all
Belong to the scope of protection of the invention.
The invention provides a kind of Thin Film Flows dynamic formula photoelectric detector, including：Sample cell, the sample cell is provided with sample
Solution inlet port is exported with sample solution；The bottom of the sample cell is have transparent working electrode；The lower section of the working electrode
It is provided with LED/light source；It is provided with the sample cell to electrode and reference electrode；The surface of the working electrode is coated with carbon
Nitrogen/titanium dioxide composite nano material, carbon nitrogen/zinc oxide compound nano material, carbon dust/titanium dioxide composite nano material, stone
One or more in black alkene/titanium dioxide composite nano material and Graphene/zinc oxide compound nano material.
According to the present invention, the sample cell is closed shading system；The sample cell is provided with sample solution import and sample
Product taphole；Exported by sample solution import and sample solution, make sample solution that current system is formed in sample cell.
The bottom of the sample cell is transparent working electrode, print solution is flow through from working electrode surface；The work
The area for making electrode is preferably 1～200mm2, more preferably 25～200mm2, it is further preferably 25～150mm2, most preferably 25～
127.17mm2；The surface of the working electrode is coated with carbon nitrogen/composite titania material, carbon nitrogen/zinc oxide compound nano material
Material, carbon dust/titanium dioxide composite nano material, Graphene/titanium dioxide composite nano material and Graphene/zinc oxide are compound to be received
One or more in rice material；Its coated weight is preferably 0.0005～0.1mg/mm2, more preferably 0.0005～0.01mg/
mm2, it is further preferably 0.0005～0.004mg/mm2, most preferably 0.0007～0.004mg/mm2。
Wherein, the carbon nitrogen/titanium dioxide composite nano material is preferably prepared in accordance with the following methods：By carbonitride, trivalent
Titanium salt, hydrogen peroxide mix with anion surfactant in water, and heating response obtains intermediate product；By the intermediate product
Calcine in protective atmosphere, obtain carbon nitrogen/titanium dioxide composite nano material.
The present invention is not particularly limited to the source of all raw materials, is commercially available or self-control.
Wherein, the carbonitride is carbonitride well known to those skilled in the art, has no special restriction, the present invention
In preferably prepare in accordance with the following methods：Melamine is calcined in protective atmosphere high temperature, carbonitride is obtained.
According to the temperature of the calcining present invention preferably employs temperature programming melamine reaches a high temperature；The liter that described program heats up
Warm speed is preferably 2～5Kmin-1, more preferably 2～3Kmin-1, it is further preferably 2.5Kmin-1；The high-temperature calcination
Temperature be preferably 500 DEG C～600 DEG C；The time of the high-temperature calcination is preferably 1～4h, more preferably 2～3h；The protection
Atmosphere is protective atmosphere well known to those skilled in the art, has no special restriction.
Room temperature is preferably cooled to after high-temperature calcination, with alcoholic solvent and water washing, then is dried；The alcoholic solvent is ability
Alcoholic solvent known to field technique personnel, has no special restriction, and the present invention is preferably methyl alcohol and/or ethanol；The drying
Temperature be preferably 60 DEG C～80 DEG C, more preferably 70 DEG C～80 DEG C；The time of the drying is preferably 10～15h, more preferably
For 12～14h.
After drying, preferably by product ultrasonic disperse to water, natural subsidence, centrifuging and taking supernatant liquor obtains carbonitride.
Carbonitride, trivalent titanium salt, hydrogen peroxide are mixed with anion surfactant in water；The titanium salt is this area
Titanium salt known to technical staff, has no special restriction, and titanium trichloride is preferably in the present invention；The carbonitride and trivalent
The ratio of titanium salt is preferably 1g：(2～4) mol；The anion surfactant is anion well known to those skilled in the art
Surfactant, has no special restriction, is preferably alkyl sulfonates surfactant in the present invention, and more preferably ten
Dialkyl benzene sulfonic acids sodium；The carbonitride is preferably 3 with the mass ratio of anion surfactant：(1.5～2.5).At this
In bright, preferred carbonitride is mixed with anion surfactant in water, is then adding titanium salt and hydrogen peroxide；It is described mixed
The time for closing stirring is preferably 0.5～2h, is further preferably 1～1.5h；The trivalent titanium salt is preferably added in form of an aqueous solutions,
The concentration of trivalent titanium ion is preferably 0.3～1mol/L, more preferably 0.4～0.8mol/L in the titanous saline solution,
It is further preferably 0.6mol/L.In the present invention, anion surfactant can promote dispersion of the carbonitride in water, may also provide
Negative electrical charge is conducive to the absorption of trivalent titanium ion, and then the titanium dioxide high density for making to be formed is uniformly distributed on carbonitride.
After mixing, heating response；The temperature of the heating response is preferably 80 DEG C～100 DEG C, and more preferably 90 DEG C～100
DEG C, it is further preferably 90 DEG C；The time of the heating response is preferably 10～30h, more preferably 12～25h, further preferably for 14～
20h, most preferably 16～18h.
After heating response, preferably with alcoholic solvent and water washing, after being dried, intermediate product is obtained；The alcoholic solvent is ability
Alcoholic solvent known to field technique personnel, has no special restriction, and methyl alcohol and/or ethanol are preferably in the present invention；It is described dry
Dry temperature is preferably 60 DEG C～80 DEG C, more preferably 70 DEG C～80 DEG C；The time of the drying is preferably 10～15h, more excellent
Elect 12～14h as.
The intermediate product is calcined in protective atmosphere；The protective atmosphere is protection well known to those skilled in the art
Atmosphere, has no special restriction, and nitrogen is preferably in the present invention；The temperature of the calcining is preferably 400 DEG C～500 DEG C；
The time of the calcining is preferably 1～4h, more preferably 2～3h, is further preferably 2h.
After calcining, by product alcoholic solvent and water washing, after being dried, carbon nitrogen/composite titania material is obtained；The alcohol
Solvent is alcoholic solvent well known to those skilled in the art, has no special restriction, and methyl alcohol and/or second are preferably in the present invention
Alcohol；The temperature of the drying is preferably 60 DEG C～80 DEG C, more preferably 70 DEG C～80 DEG C；The time of the drying is preferably 10～
15h, more preferably 12～14h.
Present invention growth in situ titanium dioxide nano-particle on carbonitride, then calcining makes its crystal formation in protective atmosphere
Change, so as to make the carbon nitrogen/titanium dioxide composite nano material for obtaining to be used for antioxidant antioxygen as photoelectric material
Change the measure of capacity.
To make, Thin Film Flows dynamic formula photoelectric detector is repeatable to be utilized, the working electrode be preferably placed at the bottom of sample cell and
Replaceable, now in order to ensure the sealing of sample cell, the working electrode preferably passes through O-ring seal with the side wall of sample cell
It is connected.
LED/light source is provided with below the working electrode, sample solution is adopted while flowing through from working electrode surface
LED/light source is irradiated；The power of the LED/light source is preferably 1000～5000mW/cm2。
It is provided with the sample cell to electrode and reference electrode；Wherein, described is that those skilled in the art are ripe to electrode
Know to electrode, have no special restriction, platinum filament, platinized platinum, titanium sheet or carbon plate are preferably in the present invention；It is described to electrode
Area is preferably 1～80mm2, more preferably 10～80mm2, it is further preferably 10～60mm2；The reference electrode is this area skill
Reference electrode known to art personnel, has no special restriction, and Ag/AgCl or saturated calomel electrode are preferably in the present invention；
Wherein described Ag/AgCl reference electrodes are preferably Ag/AgCl (3mol/L KCl) or Ag/AgCl (saturation KCl).
The photoelectric detector that the present invention is provided is easy to operate, with low cost, can promptly carry out antioxidant antioxidant capacity
Detection；The incidence of its light source is back reflection type, can maximize the impact for avoiding colored samples background signal.In addition Thin Film Flows
The introducing of dynamic formula sample introduction, not only contributes to measure photoelectric current and keeps constant, and improves mass transfer ability, and sensitivity is carried significantly
Rise.
Present invention also offers a kind of detection method of antioxidant capacity, comprises the following steps：
Using above-mentioned Thin Film Flows dynamic formula photoelectric detector；Testing sample solution is injected into sample by sample solution import
Chi Zhong, carries out the detection of antioxidant capacity.
Wherein, the Thin Film Flows dynamic formula photoelectric detector is same as above, will not be described here.
Testing sample solution is injected in sample cell by sample solution import；The injection flow velocity of the testing sample solution
Preferably 0.1～50ml/min, more preferably 1～50ml/min, are further preferably 10～50ml/min, most preferably 10～
45ml/min；The operating voltage of the working electrode be preferably -0.2～0.4V, more preferably -0.1～0.4V, further preferably for -
0.1～0.2V；The wavelength of the LED/light source is preferably 380～560nm, more preferably 380～500nm, further preferably for 400～
480nm。
In order to further illustrate the present invention, the present invention is provided a kind of Thin Film Flows dynamic formula photoelectricity inspection with reference to embodiments
The detection method for surveying device and antioxidant capacity is described in detail.
In following examples reagent used be it is commercially available (carbonitride synthesis Program heat up heating rate be 2.5K
min-1)。
Embodiment 1
The synthesis of 1.1 ultra-thin carbonitrides：
Weigh 2 grams of melamines to be put in crucible, 500 DEG C are heated under nitrogen atmosphere, constant temperature 2 hours is subsequently cooled down
To room temperature.With methyl alcohol, secondary water difference centrifuge washing for several times, and in 70 DEG C of dryings 12 hours, the carbonitride of body is obtained (referred to as
bg-C3N4).By in products therefrom ultrasonic disperse to secondary water, solution natural subsidence is made, it is standby to be then centrifuged for taking supernatant, obtains final product
To ultra-thin carbonitride (abbreviation utg-C3N4)；
The synthesis of 1.2 ultra-thin carbon nitrogen/composite titania materials：
Respectively by 3 milligrams of utg-C3N4It is dispersed in secondary water with 1.5 milligrams of dodecyl sodium sulfates, uniform stirring 1 is little
When.And then 10 milliliters of titanium trichlorides (0.6 mole per liter) and 5 milliliters of hydrogen peroxide (mass fraction 1%) are rapidly added respectively
Above-mentioned solution, reacts 16 hours at 90 DEG C.The precipitation of generation uses ethanol, secondary water centrifuge washing for several times respectively, and dry in 70 DEG C
Dry 12 hours.Then above-mentioned dry products are heated to into 400 DEG C of constant temperature 2 hours, products therefrom ethanol, secondary water washing number
Secondary, final 70 DEG C of dryings obtain ultra-thin carbon nitrogen/titanium dioxide composite nano material (abbreviation utg-C for 12 hours3N4/TiO2)。
Fig. 1 is the dispersion liquid picture of the carbonitride with ultra-thin carbonitride of the body obtained in embodiment 1.As shown in Figure 1,
Bg-C after fortnight3N4Great majority precipitation, and utg-C3N4Remain in that clarification.Illustrate utg-C3N4With preferable dispersiveness.
(A, A1 are bg-C in Fig. 13N4Dispersion liquid, B, B1 are utg-C3N4Dispersion liquid).
The ultra-thin carbonitride obtained in embodiment 1 is analyzed using AFM, is obtained its atomic force and is shown
Micro mirror photo is as shown in Fig. 2 obtain its force curve of atomic force microscope figure such as Fig. 3.
The ultra-thin carbonitride obtained in embodiment 1 is analyzed using transmission electron microscope, obtains its transmission electron microscope photo,
As shown in Figure 4.
It is analyzed using the carbonitride of body of the transmission electron microscope to obtaining in embodiment 1, obtains its transmission electron microscope photo,
As shown in Figure 5.
Carbon nitrogen/the titanium dioxide composite nano material obtained in embodiment 1 is analyzed using transmission electron microscope, obtains it
Transmission electron microscope photo, as shown in Figure 6.
Carbon nitrogen/the titanium dioxide composite nano material obtained in embodiment 1 is analyzed using high-resolution-ration transmission electric-lens,
Its high-resolution-ration transmission electric-lens photo is obtained, as shown in Figure 7.
Using the carbonitride of body of the X-ray diffraction to obtaining in embodiment 1, ultra-thin carbonitride and carbon nitrogen/titanium dioxide
Titanium composite nano materials are analyzed, and its X-ray diffraction spectrogram are obtained, shown in Fig. 8.
The ultra-thin carbonitride obtained in embodiment 1 is combined with carbon nitrogen/titanium dioxide using x-ray photoelectron spectroscopy
Nano material is analyzed, and obtains its x-ray photoelectron energy spectrum diagram, as shown in Figure 9.
Figure 10 is TiO2(a0, a1), bg-C3N4/TiO2(b0, b1) and utg-C3N4/TiO2The light of (c0, c1) three kinds of materials
Electroresponse signal graph.A0, b0 and c0 are the responses in blank phosphate buffer solution (0.1 mole of every liter of pH=7.4), apply current potential
For 0 volt, light source is the photoelectric current of 420 nanometers of LED (3 watts), after adding every liter of gallic acid of 50 micromole, the light of three kinds of materials
Electric current all increases sharply (a1, b2 and c3), wherein after either blank or addition antioxidant gallic acid, utg-C3N4/
TiO2Photoelectric current be all significantly higher than other control materials, illustrate utg-C3N4/TiO2It is one preferably anti-for antioxidant
The photoelectric material that oxidation capacity is determined.
Embodiment 2
The preparation of 2.1 working electrodes
Carbon nitrogen/titanium dioxide (the utg-C for selecting embodiment 1 to prepare3N4/TiO2) composite nano materials be photoelectric material.Will
utg-C3N4/TiO2Ultrasonic disperse (1mg/mL) in secondary water, takes the above-mentioned dispersion liquid coatings of 100 μ L electric to the ITO of particular area
Extremely go up, first spontaneously dry and then solidify within 1 hour in 70 DEG C of dryings, obtain the working electrode of Photoelectric Detection.Platinum filament is selected to be to electricity
Pole, Ag/AgCl (3mol/L) is reference electrode, working electrode and is respectively 127.17mm to electrode area2And 56.52mm2。
2.2 design laminar flows Photoelectric Detection ponds
Electrode, reference electrode and working electrode will be fixed in flow cell, wherein working electrode is removable, sample
Input mode adopts Flow Sampling, and is integrated with LED light source interface, and the structural representation of Thin Film Flows dynamic formula photoelectric detector is as schemed
Shown in 11.
2.3 setup parameter
Selection operating potential be 0V, sample feeding flow velocity (10mL/min), in 420nm LED (light source power 5000mW/
cm2) illumination under antioxidant antioxidant capacity is measured.
2.4 are detected
1000 times of proline, glycine, histidine, methyl alcohol and ethanol, 500 times of threonine, fructose, glucose, lemon
Lemon acid and malic acid, detect under conditions of 20 times of cysteine presence to 25mmol/L gallic acids, obtain it anti-dry
Measurement result figure is disturbed, as shown in figure 12.
Embodiment 3
The preparation of 3.1 working electrodes
Carbon nitrogen/titanium dioxide (the utg-C for selecting embodiment 1 to prepare3N4/TiO2) composite nano materials be photoelectric material.Will
utg-C3N4/TiO2Ultrasonic disperse (1mg/mL) in secondary water, takes the above-mentioned dispersion liquid coatings of 100 μ L electric to the ITO of particular area
Extremely go up, first spontaneously dry and then solidify within 1 hour in 70 DEG C of dryings, obtain Photoelectric Detection working electrode.Select platinum filament be to electrode,
Ag/AgCl (3mol/L) is reference electrode, working electrode and is respectively 127.17mm to electrode area2And 56.52mm2。
3.2 design laminar flows Photoelectric Detection ponds
Electrode, reference electrode and working electrode will be fixed in flow cell, wherein detection working electrode is removable,
Sample feeding mode adopts Flow Sampling, and is integrated with LED light source interface, and the structural representation in laminar flows Photoelectric Detection pond is such as
Shown in Figure 11.
3.3 setup parameter
Selection operating potential be 0V, sample feeding flow velocity (10mL/min), in 420nm LED (light source power 5000mW/
cm2) illumination under antioxidant antioxidant capacity is measured.
3.4 are detected
The antioxidant of nine kinds of standards is measured, wherein caffeic acid, theophylline and ascorbic acid three kinds of antioxidants
Response is as shown in figure 13, wherein being followed successively by caffeic acid, theophylline and ascorbic acid from left to right, responds in the wider range of linearity
Well.Remaining the results are shown in Table 1.
The standard anti-oxidant testing result of table 1
Note：Each sample determination is averaged for three times.
Embodiment 4
The preparation of 4.1 working electrodes
Carbon nitrogen/titanium dioxide (the utg-C for selecting embodiment 1 to prepare3N4/TiO2) composite nano materials be photoelectric material.Will
utg-C3N4/TiO2Ultrasonic disperse (1mg/mL) in secondary water, takes the above-mentioned dispersion liquid coatings of 100 μ L electric to the ITO of particular area
Extremely go up, first spontaneously dry and then solidify within 1 hour in 70 DEG C of dryings, obtain Photoelectric Detection working electrode.Select platinum filament be to electrode,
Ag/AgCl (3mol/L) is reference electrode, working electrode and is respectively 127.17mm to electrode area2And 56.52mm2。
4.2 design laminar flows Photoelectric Detection ponds
Electrode, reference electrode and working electrode will be fixed in flow cell, wherein detection working electrode is removable,
Sample feeding mode adopts Flow Sampling, and is integrated with LED light source interface, and the structural representation in laminar flows Photoelectric Detection pond is such as
Shown in Figure 11.
4.3 setup parameter
Selection operating potential be 0V, sample feeding flow velocity (10mL/min), in 420nm LED (light source power 5000mW/
cm2) illumination under antioxidant antioxidant capacity is measured.
4.4 are detected
It is consistent with two kinds of spectroscopic methodology results to four kinds of commercial tealeaves and coffee total antioxidation solid measure result, measurement knot
Fruit is as shown in table 2.Two kinds of measuring methods are as follows：
(a) F-C methods：The tealeaves of the various diluted concentrations of 100 μ L and coffee are added in the centrifuge tube of 2mL, are then added respectively
Enter 200 μ L F-C reagents (10%, v/v) and 800 μ L sodium carbonate liquors, 20 DEG C of reaction 2h, uv-vis spectra records 760nm's
Absorbance.
(b) DPPH methods：The tealeaves of the various diluted concentrations of 200 μ L and coffee are added in the centrifuge tube of 2mL, are subsequently adding
800 μ L DPPH solution (40mg/L), react 15min in the case of lucifuge, uv-vis spectra records the absorbance of 514nm.
The commercial tealeaves of 2 four kinds of table and coffee total antioxidation solid measure result
Note：Each sample determination is averaged for three times；GA：Gallic acid；TROLOX：Water soluble vitamin
Embodiment 5
The preparation of 5.1 working electrodes
Select carbon dust/titanium dioxide (C/TiO2) composite nano materials be photoelectric material.By C/TiO2The ultrasound in secondary water
Dispersion, takes the above-mentioned dispersion liquid coatings of 100 μ L in the ITO electrode of particular area, first spontaneously dries and then in 70 DEG C of dryings 1 hour
Solidification, obtains the working electrode of Photoelectric Detection.Platinum filament is selected to be that, to electrode, saturated calomel electrode (SCE) is reference electrode, is worked
Electrode and 80mm is respectively to electrode area2And 60mm2。
5.2 design laminar flows Photoelectric Detection ponds
Electrode, reference electrode and working electrode will be fixed in flow cell, wherein detection working electrode is removable,
Sample feeding mode adopts Flow Sampling, and is integrated with LED light source interface, and the structural representation in laminar flows Photoelectric Detection pond is such as
Shown in Figure 11.
5.3 setup parameter
Selection operating potential be 0.2V, sample feeding flow velocity (20mL/min), in 480nm LED (light source power 5000mW/
cm2) illumination under antioxidant antioxidant capacity is measured.
5.4 are detected
It is consistent with two kinds of spectroscopic methodology results to four kinds of commercial tealeaves total antioxidation solid measure results, measurement result such as table
Shown in 3.
The commercial tealeaves total antioxidation solid measure result of 3 four kinds of table
Note：Each sample determination is averaged for three times；GA：Gallic acid；TROLOX：Water soluble vitamin.
Embodiment 6
The preparation of 6.1 working electrodes
Selection Graphene/zinc oxide (G/ZnO) composite nano materials are photoelectric material.G/ZnO is ultrasonic in secondary water
Dispersion, takes the above-mentioned dispersion liquid coatings of 100 μ L in the ITO electrode of particular area, first spontaneously dries and then in 70 DEG C of dryings 1 hour
Solidification, obtains Photoelectric Detection working electrode.Platinum filament is selected to be that, to electrode, Ag/AgCl (saturation KCl) is reference electrode, work is electric
Pole and 25mm is respectively to electrode area2And 10mm2。
6.2 design laminar flows Photoelectric Detection ponds
Electrode, reference electrode and working electrode will be fixed in flow cell, wherein detection working electrode is removable,
Sample feeding mode adopts Flow Sampling, and is integrated with LED light source interface, and the structural representation in laminar flows Photoelectric Detection pond is such as
Shown in Figure 11.
6.3 setup parameter
Selection operating potential is -0.1V, sample feeding flow velocity 450mL/min, in 400nm LED (light source power 5000mW/
cm2) illumination under antioxidant antioxidant capacity is measured.
6.4 are detected
It is consistent with two kinds of spectroscopic methodology results to four kinds of commercial coffee total antioxidation solid measure results, measurement result such as table
Shown in 4.
The commercial coffee total antioxidation solid measure result of 4 four kinds of table
Note：Each sample determination is averaged for three times；GA：Gallic acid；TROLOX：Water soluble vitamin.
Claims (10)
1. a kind of Thin Film Flows dynamic formula photoelectric detector, it is characterised in that include：Sample cell, it is molten that the sample cell is provided with sample
Liquid import is exported with sample solution；The bottom of the sample cell is transparent working electrode；The lower section of the working electrode is arranged
There is LED/light source；It is provided with the sample cell to electrode and reference electrode；The surface of the working electrode is coated with carbon nitrogen/bis-
Titanium oxide composite nano materials, carbon nitrogen/zinc oxide compound nano material, carbon dust/titanium dioxide composite nano material, Graphene/
One or more in titanium dioxide composite nano material and Graphene/zinc oxide compound nano material.
2. Thin Film Flows dynamic formula photoelectric detector according to claim 1, it is characterised in that the area of the working electrode is
1～200mm2；The area to electrode is 1～80mm2。
3. Thin Film Flows dynamic formula photoelectric detector according to claim 1, it is characterised in that described is platinum filament, platinum to electrode
Piece, titanium sheet or carbon plate；The reference electrode is Ag/AgCl or saturated calomel electrode.
4. Thin Film Flows dynamic formula photoelectric detector according to claim 1, it is characterised in that the carbon nitrogen/titanium dioxide is multiple
Condensation material is prepared in accordance with the following methods：
Melamine is calcined in protective atmosphere high temperature, ultrasonic disperse obtains carbonitride in water；
Carbonitride, trivalent titanium salt, hydrogen peroxide are mixed with anion surfactant in water, heating response obtains middle product
Thing；
The intermediate product is calcined in protective atmosphere, carbon nitrogen/composite titania material is obtained.
5. Thin Film Flows dynamic formula photoelectric detector according to claim 4, it is characterised in that the carbonitride and trivalent titanium salt
The ratio of middle titanium ion is 1g：(2～4) mol；The carbonitride is 3 with the mass ratio of anion surfactant：(1.5～
2.5)。
6. Thin Film Flows dynamic formula photoelectric detector according to claim 4, it is characterised in that the temperature of the heating response is
80 DEG C～100 DEG C；The time of the heating response is 10～30h；The temperature of the calcining is 400 DEG C～500 DEG C；The calcining
Time be 1～4h.
7. a kind of detection method of antioxidant capacity, it is characterised in that comprise the following steps：
Using the Thin Film Flows dynamic formula photoelectric detector described in claim 1～6 any one；
Testing sample solution is injected in sample cell by sample solution import, the detection of antioxidant capacity is carried out.
8. detection method according to claim 7, it is characterised in that the operating voltage of the working electrode is -0.2～
0.4V。
9. detection method according to claim 7, it is characterised in that the injection flow velocity of the testing sample solution is 0.1
～50ml/min.
10. detection method according to claim 7, it is characterised in that the wavelength of the LED/light source is 380～560nm.
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| CN110879241A (en) * | 2019-12-10 | 2020-03-13 | 南阳理工学院 | Thin-layer flow type photoelectric detector and method for detecting oxidation resistance capacity |
| CN111847905A (en) * | 2020-07-09 | 2020-10-30 | 南昌航空大学 | Preparation method of thin-layer flow cell for ultraviolet and visible light absorption test |
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| CN111847905A (en) * | 2020-07-09 | 2020-10-30 | 南昌航空大学 | Preparation method of thin-layer flow cell for ultraviolet and visible light absorption test |
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