CN102967570A - Method for detecting photochemical activity of carbon nano tube by utilizing transient absorption spectrum technology - Google Patents
Method for detecting photochemical activity of carbon nano tube by utilizing transient absorption spectrum technology Download PDFInfo
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Abstract
The invention relates to a method for detecting photochemical activity of a carbon nano tube by utilizing a transient absorption spectrum technology and belongs to the field of photochemical activity detection of carbon nano tubes. The method comprises the following steps: a, preparing aqueous solution of the carbon nano tube, ultrasonically treating the aqueous solution of the carbon nano tube, standing, and taking supernatant liquid of the aqueous solution of the carbon nano tube as a detection object; b, analyzing photochemical properties of the aqueous solution of the carbon nano tube under illumination conditions by utilizing a laser flash photolysis instrument; and c, verifying and analyzing a characteristic peak of the transient absorption spectrum of the carbon nano tube obtained by the laser flash photolysis instrument in step b by utilizing a pulse radiolysis device. According to the detection method, aiming at a special carbon-based nano material such as the carbon nano tube, the photochemical activity particles in the aqueous solution can be conveniently and reliably detected, the carbon nano tube is insensitive to interference of an external environment, and a carbon nano tube sample is not required to be excessively modified and treated in the earlier stage.
Description
Technical field
The invention belongs to carbon nano-tube photochemical activity detection field, more particularly, relate to a kind of transient absorption spectroscopy that utilizes and detect the photochemically reactive method of carbon nano-tube.
Background technology
Carbon nano-tube and adamas, graphite, fullerene are the same, also are a kind of allotropes of carbon.It is a kind of tube wall molecule that is elongate tubular, generally is to arrange the coaxial pipe that then connection curls into by carbon atom in hexagonal mode.If pipe only is comprised of the carbon atom of individual layer and then is called Single Walled Carbon Nanotube, when being comprised of the carbon atomic layer of multilayer, pipe then is called multi-walled carbon nano-tubes.Carbon nano-tube has that specific surface area is large, hardness is high and the characteristics such as thermally-stabilised.In addition, owing to it is developed by graphite, exist a lot of not paired free electrons at its tube wall, so carbon nano-tube also has electric conductivity and the semi-conductive character of metal.Although since being found from carbon nano-tube in 1991, researcher has carried out a lot of research to the physicochemical property of carbon nano-tube, in default of effective detection method, the spectrochemical property of carbon nano-tube in aqueous solution is still had little understanding.
The technology of existing detection carbon nano-tube spectrochemical property mainly comprises: chromatography, electron spin resonance (EPR), chemoluminescence method, potentiometric titration.These methods belong to the stable state detection technique, and its general principle is to detect the variation that brings to surrounding environment after optical excitation material to be detected reacts, and proves indirectly by checking this variation whether material to be detected has photocatalysis or photoresponse ability.These detection methods existence under the steady state conditions are subject to the surrounding environment interference, inspection process is complicated, testing accuracy is low, the shortcoming of length consuming time.Simultaneously, because carbon nano-tube is water insoluble, and has again very strong capture ability to most free radical, the detection method under the existing steady state conditions can't conclude fast and accurately all whether carbon nano-tube has the photoresponse ability in specific solution system.Therefore, seek a kind of can be easy and photochemical activity that reliable method detects carbon nano-tube seems particularly important.
Transient absorption spectroscopy detects (comprising laser flash photolysis and radiolysis) a kind of effective means of short life active particle beyond doubt.Adopt time-resolved laser flash photolysis and radiolysis, from the start with microscopic nature of research charge transfer process of molecule and electronic horizon, the information of the microcosmic ultrafast response essence that can't obtain with other method be can obtain, chemistry and life science promoted to the dynamic quantitative future development.Material is subjected to after the optical excitation by ground state transition in its attenuation process a series of variation and reaction can to occur to excited state, utilizes time-resolved laser flash photolysis instrument can observe transient state spectrum in these change procedures.Can be to the excited singlet state in the course of reaction, triplet molecule by time-resolved absorption and emission transient state spectrum and corresponding dynamics die-away curve, the transient response such as free radical and positive and negative ion intermediate etc. is studied (Yu Qun, the leaf Jianping, Shou Hansen. the brief introduction of laser flash photolysis technology.The chemistry circular, 1989,5,51-53.).Radiation chemistry is identical with photochemical primary process essence: after radiation energy or luminous energy are passed to medium molecule, all may produce ion, electronics, excite molecule, free radical etc.The pulse radiolysis aqueous solution can make hydrone dissociate and produce a large amount of hydroxyl radical free radicals (OH), aqueous electron (e
Aq -) and hydroperoxyl radical (H) isoreactivity particle.Aqueous solution by can the gating pulse radiolysis to the regulation and control of experiment condition produces oxidisability or reductibility environment.Active particle wherein can with the carbon nano-tube effect, the kation of Formed nanotube or radical anion, thus the transient state particle that produces under Ear Mucosa Treated by He Ne Laser Irradiation for carbon nano-tube aqueous solutions provides evidence.
Transient absorption spectroscopy has been widely used in chemistry and life science, such as electronics (proton) in the molecule shift, the photosynthesis of biomolecule etc.Because the characteristic of light absorption techniques self, the system of research is generally true solution.For water-insoluble carbon nano-tube, the researcher has taked carbon nano tube surface is modified the measure of processing, make it water soluble, and then utilize transient absorption spectroscopy to detect (M. Alvaro, P. Atienzar, P. de la Cruz, J.L. Delgado, H. Garcia, F. Langa. Synthesis and photochemistry of soluble, pentyl ester-modified single wall carbon nanotube. Chemical Physics Letters, 2004,386,342-345.), but the photochemistry pickup electrode of observing thus may be subjected to the impact of bonding molecule or the functional group of introducing.
Summary of the invention
The problem that solves
Can't fast and accurately judge all for the detection method under the existing steady state conditions whether carbon nano-tube has the problem of photoresponse ability in specific solution system, the invention provides a kind of transient absorption spectroscopy that utilizes and detect the photochemically reactive method of carbon nano-tube, can detect easy, reliably its photochemical activity particle in aqueous solution for this special c-based nanomaterial of carbon nano-tube, the interference of environment is insensitive to external world, and do not need the carbon nano-tube sample is carried out too much modification and processing early stage yet.
Technical scheme
In order to address the above problem, the technical solution adopted in the present invention is as follows:
A kind of transient absorption spectroscopy that utilizes detects the photochemically reactive method of carbon nano-tube, and the method may further comprise the steps:
A. prepare carbon nano-tube aqueous solutions, carbon nano-tube aqueous solutions is processed through ultrasound wave, and the supernatant liquor of getting carbon nano-tube aqueous solutions after leaving standstill is detected object;
B. utilize the laser flash photolysis instrument that carbon nano-tube aqueous solutions is resolved at the spectrochemical property under the illumination condition;
C. utilize pulse radiolysis apparatus that the carbon nano-tube transient absorption spectrum that laser flash photolysis instrument among the step b obtains is carried out the check analysis of characteristic peak.
Preferably, the time of the processing of the ultrasound wave among the described step a is 1-2 h.
Preferably, the carbon nano-tube among the described step a is Single Walled Carbon Nanotube, multi-walled carbon nano-tubes and surface-functionalized carbon nano-tube.Carbon nano-tube does not need extra modification to process also need not add stabilizer treatment.
Preferably, the spectrogram that the laser flash photolysis instrument obtains among the described step b comprises transient absorption spectra that carbon nano-tube produces and at certain wave strong point decay spectra in time under excitation source.
Further, the check analysis of described step c is to carry out respectively under oxidation and the reductive condition at carbon nano-tube aqueous solutions.
Preferably, described reductive condition is to the logical N of carbon nano-tube aqueous solutions
2Gas to the saturated and tert-butyl alcohol that adds 1 ~ 2 mmol/L to remove the aqueous solution ionization hydroxyl radical free radical that radiolysis was produced; The oxidisability condition is to the logical N of carbon nano-tube aqueous solutions
2O gas ionizes the aqueous electron that radiolysis was produced to saturated to remove aqueous solution.
Preferably, the supernatant liquor to be detected of carbon nano-tube aqueous solutions also passes through Air Exposure among the described step a, and described Air Exposure is directly to carry out in the sample cell with the experimental apparatus of sealed membrane good seal.
Beneficial effect
Than prior art, beneficial effect of the present invention is:
(1) the present invention processes through ultrasound wave carbon nano-tube aqueous solutions, the supernatant liquor of getting carbon nano-tube aqueous solutions after leaving standstill is detected object, used carbon nano-tube is not needed to carry out extra chemical modification processing again need not add any stable chemical reagent of carbon nano-tube that helps yet, therefore the present invention can get rid of the impact of non-carbon nano-tube material, and is more directly perceived, detect the spectrochemical property of carbon nano-tube exactly;
(2) the present invention utilizes the laser flash photolysis instrument that carbon nano-tube aqueous solutions is resolved at the spectrochemical property under the illumination condition, can clearly observe chemical reaction that carbon nano-tube occurs in the short time after Stimulated Light irradiation and the existence of reaction product;
(3) the present invention utilizes pulse radiolysis apparatus that the carbon nano-tube transient absorption spectrum that laser flash photolysis instrument among the step b obtains is carried out the check analysis of characteristic peak, the transient absorption spectra data that produced under specific oxidation or reductive condition take the pulse radiolysis with same time resolution can accurately be judged the product kind that carbon nano-tube generates as contrast under illumination condition;
(4) check analysis of the present invention is to carry out respectively under oxidation and the reductive condition at carbon nano-tube aqueous solutions, and reductive condition is to the logical N of carbon nano-tube aqueous solutions
2Gas is to saturated and add an amount of tert-butyl alcohol; The oxidisability condition is to the logical N of carbon nano-tube aqueous solutions
2O gas is to saturated, and resulting experimental solutions condition difference is remarkable thus, thereby makes the result accurately and reliably, and condition control is simple, and testing cost is low.
Description of drawings
Fig. 1 is that Single Walled Carbon Nanotube (S-SWNT) aqueous solution is at laser photolysis (LFP) transient absorption spectra of several time points;
Fig. 2 is that Single Walled Carbon Nanotube (S-SWNT) aqueous solution generates and die-away curve in the dynamics of 420 nm places record after laser photolysis;
Fig. 3 is that Single Walled Carbon Nanotube (S-SWNT) aqueous solution adds the tert-butyl alcohol and logical N
2To saturated rear (PR reduction) and logical N
2O gas is to saturated rear (PR oxidation), and the dynamics of being tested the 420 nm places that obtain by pulse radiolysis (PR) generates and die-away curve;
Fig. 4 is that multi-walled carbon nano-tubes (MWNT-OH) aqueous solution is at laser photolysis (LFP) the transient absorption spectra figure of several time points;
Fig. 5 is that multi-walled carbon nano-tubes (MWNT-OH) aqueous solution generates and die-away curve in the dynamics of 380 nm places record after laser photolysis;
Fig. 6 is that multi-walled carbon nano-tubes (MWNT-OH) aqueous solution adds the tert-butyl alcohol and logical N
2Gas is to saturated rear (PR reduction) and logical N
2O gas is to saturated rear (PR oxidation), and the dynamics at the 380nm place that is obtained by pulse radiolysis (PR) experiment generates and die-away curve.
Embodiment
The present invention will be further described in detail below in conjunction with specific embodiment.
Embodiment 1
A kind of transient absorption spectroscopy that utilizes detects the photochemically reactive method of carbon nano-tube, and the method may further comprise the steps:
A. prepare carbon nano-tube aqueous solutions, take by weighing 1 mg Single Walled Carbon Nanotube (S-SWNT) and be dissolved in the 25 mL ultrapure waters, with the ultrasonic processing of supersonic cleaning machine.The purpose that adopts ultrasound wave to process be for better with carbon nanotube dispersed in aqueous solution.In general, ultrasonic time is longer, and the effect of carbon nanotube dispersed is better.The carbon nano-tube ultrasonic jitter time required than the protoplasm carbon nano-tube that hydroxyl, carboxyl isopolarity functional group are contained in the surface will be lacked.So the time that ultrasound wave is processed be 1-2 h all can, present embodiment preferably selects ultrasound wave to process 2 h.The supernatant liquor of getting carbon nano-tube aqueous solutions after leaving standstill is detected object; Through Air Exposure, Air Exposure is directly to carry out in the sample cell with the experimental apparatus of sealed membrane good seal with supernatant liquor to be detected.
B. utilize the laser flash photolysis instrument that carbon nano-tube aqueous solutions is resolved at the spectrochemical property under the illumination condition; Carbon nano-tube aqueous solutions 2 mL that get the preparation of a step move in the sample cell of laser flash photolysis instrument, then carry out the laser photolysis experiment.
C. utilize pulse radiolysis apparatus that the carbon nano-tube transient absorption spectrum that laser flash photolysis instrument among the step b obtains is carried out the check analysis of characteristic peak.Check analysis is to carry out respectively under oxidation and the reductive condition at carbon nano-tube aqueous solutions.Reductive condition is to the logical N of carbon nano-tube aqueous solutions
2Gas is extremely saturated and add an amount of tert-butyl alcohol to remove the aqueous solution ionization hydroxyl radical free radical that radiolysis was produced; The oxidisability condition is to the logical N of carbon nano-tube aqueous solutions
2O gas ionizes the aqueous electron that radiolysis was produced to saturated to remove aqueous solution.The concrete operations of present embodiment oxidation and reductive condition are respectively: (1) gets carbon nano-tube aqueous solutions 2 mL of a step preparation in the sample cell of impulse radiation device, add the hydroxyl radical free radical that 1 mmol/L tert-butyl alcohol selective removal water radiolysis produces, and pass into high-purity N
220 min are to remove dissolved oxygen DO, and the active particle under this condition in the solution is mainly aqueous electron, and solution is the reductibility environment; (2) carbon nano-tube aqueous solutions 2 mL that get the preparation of a step lead to N in the sample cell of pulse radiolysis
2O gas 20 min are with the selective removal aqueous electron, and the active particle under this condition in the solution is mainly hydroxyl radical free radical, and solution is oxidative environment.
The result who obtains such as Fig. 1, Fig. 2, shown in Figure 3.Transient absorption by Fig. 1 Single Walled Carbon Nanotube (S-SWNT) laser photolysis can be found out, carbon nano-tube can generate a transient state particle that has characteristic absorption at 420 nm places under the exciting of excitation source, can find out that As time goes on this particle decays to disappearance very soon simultaneously.Generated with die-away curve in the dynamics of 420 nm places record after the laser photolysis by Fig. 2 Single Walled Carbon Nanotube (S-SWNT) aqueous solution and can find out that carbon nano-tube builds up to maximum during 1 μ s after the transient state particle of generation under the exciting of excitation source is exciting, then rapidly decay to disappearance.Pulse radiolysis transient absorption spectra by Fig. 3 can be found out: filling N
2Do not detect the product at 420 nm places under the oxidisability condition of O gas, at the interpolation tert-butyl alcohol and at logical N
2Gas has detected the product at 420 nm places to the saturated reducing solution.The product at laser photolysis gained 420 nm places has identical generation and decaying kinetics among this product and Fig. 2.Therefore, can judge that Single Walled Carbon Nanotube (S-SWNT) issues third contact of a total solar or lunar eclipse ionization exciting of pulse laser, the electronics generation solvation that ionizes out generates aqueous electron.Single Walled Carbon Nanotube (S-SWNT) is caught aqueous electron and is generated radical anion.
A kind of transient absorption spectroscopy that utilizes detects the photochemically reactive method of carbon nano-tube, and the method may further comprise the steps:
A. prepare carbon nano-tube aqueous solutions, take by weighing 1 mg surface and contain the multi-walled carbon nano-tubes (MWNT-OH) of 3.7% hydroxyl and be dissolved in the 25 mL ultrapure waters, then use ultrasonic processing 1 h of supersonic cleaning machine, leave standstill after the ultrasonic end that to get supernatant liquor be detected object.
B. utilize the laser flash photolysis instrument that carbon nano-tube aqueous solutions is resolved at the spectrochemical property under the illumination condition; Supernatant liquor 2 mL that get the carbon nano-tube aqueous solutions of a step preparation move in the sample cell of laser flash photolysis instrument, then carry out the laser photolysis experiment.
C. utilize pulse radiolysis apparatus that the carbon nano-tube transient absorption spectrum that laser flash photolysis instrument among the step b obtains is carried out the check analysis of characteristic peak.The check analysis of step c is to carry out respectively under oxidation and the reductive condition at carbon nano-tube aqueous solutions.The concrete operations of present embodiment are: (1) reductive condition, get carbon nano-tube aqueous solutions 2 mL of a step preparation in the sample cell of impulse radiation device, and add the hydroxyl radical free radical that 2 mmol/L tert-butyl alcohol selective removal water radiolysis produce, and pass into high-purity N
220 min are to remove dissolved oxygen DO.Active particle under this condition in the solution is mainly aqueous electron, is reducing atmosphere; (2) oxidisability condition is got carbon nano-tube aqueous solutions 2 mL of a step preparation in the sample cell of pulse radiolysis, passes into N
2O gas 20 min are with the selective removal aqueous electron.Active particle under this condition in the solution is mainly hydroxyl radical free radical, is oxidizing atmosphere.
The result who obtains such as Fig. 4, Fig. 5, shown in Figure 6.A plurality of characteristic absorption peaks are appearring in hydroxylated multi-walled carbon nano-tubes (MWNT-OH) between 300-450 nm after the laser photolysis as seen from Figure 4.As seen multi-walled carbon nano-tubes has the photoresponse ability in aqueous solution.Generated with die-away curve in the dynamics of 380 nm places record after the laser photolysis by Fig. 5 multi-walled carbon nano-tubes (MWNT-OH) aqueous solution and can find out that carbon nano-tube builds up to maximum during 1 μ s after the excited state particle of generation under the exciting of excitation source is exciting, then rapidly decay to disappearance.Pulse radiolysis transient absorption spectra by Fig. 6 can be found out: filling N
2Do not detect the product at 380 nm places under the oxidisability condition of O gas, adding the tert-butyl alcohol and detecting the product at 380 nm places with nitrogen in the saturated reducing solution.The product at laser photolysis gained 380 nm places has identical generation and decaying kinetics feature among Fig. 2 of this product and embodiment 1.Therefore, can judge that multi-walled carbon nano-tubes (MWNT-OH) issues third contact of a total solar or lunar eclipse ionization exciting of pulse laser, the electronics generation solvation that ionizes out generates aqueous electron.Multi-walled carbon nano-tubes (MWNT-OH) is caught aqueous electron and is generated radical anion.
Below schematically the present invention and embodiment thereof are described, this description does not have restricted, although only provided Single Walled Carbon Nanotube and the surperficial embodiment that contains the multi-walled carbon nano-tubes of 3.7% hydroxyl among the embodiment, actual application is not limited to this.Those skilled in the art can expect that according to prior art, technical scheme of the present invention and embodiment the present invention can finish the test of the photochemical activity of all carbon nano-tube, the carbon nano-tube of the functionalization such as, sulfhydrylation carboxylated such as the surface.So, if those of ordinary skill in the art is enlightened by it, in the situation that does not break away from the invention aim, without the creationary technical scheme similar to this technical scheme, application and the embodiment of designing, all should belong to protection scope of the present invention.
Claims (7)
1. one kind is utilized transient absorption spectroscopy to detect the photochemically reactive method of carbon nano-tube, it is characterized in that the method may further comprise the steps:
A. prepare carbon nano-tube aqueous solutions, carbon nano-tube aqueous solutions is processed through ultrasound wave, and the supernatant liquor of getting carbon nano-tube aqueous solutions after leaving standstill is detected object;
B. utilize the laser flash photolysis instrument that carbon nano-tube aqueous solutions is resolved at the spectrochemical property under the illumination condition;
C. utilize pulse radiolysis apparatus that the carbon nano-tube transient absorption spectrum that laser flash photolysis instrument among the step b obtains is carried out the check analysis of characteristic peak.
2. detect the photochemically reactive method of carbon nano-tube according to a kind of transient absorption spectroscopy that utilizes claimed in claim 1, it is characterized in that the time that the ultrasound wave among the described step a is processed is 1-2 h.
3. detect the photochemically reactive method of carbon nano-tube according to a kind of transient absorption spectroscopy that utilizes claimed in claim 1, it is characterized in that: the carbon nano-tube among the described step a is Single Walled Carbon Nanotube, multi-walled carbon nano-tubes and surface-functionalized carbon nano-tube.
4. detect the photochemically reactive method of carbon nano-tube according to a kind of transient absorption spectroscopy that utilizes claimed in claim 1, it is characterized in that: the spectrogram that the laser flash photolysis instrument obtains among the described step b comprises transient absorption spectra that carbon nano-tube produces and at certain wave strong point decay spectra in time under excitation source.
5. detect the photochemically reactive method of carbon nano-tube according to the described a kind of transient absorption spectroscopy that utilizes of any one in claim 1 or 2 or 3 or 4, it is characterized in that: the check analysis of described step c is to carry out respectively under oxidation and the reductive condition at carbon nano-tube aqueous solutions.
6. detect the photochemically reactive method of carbon nano-tube according to a kind of transient absorption spectroscopy that utilizes claimed in claim 5, it is characterized in that: described reductive condition is for leading to N to carbon nano-tube aqueous solutions
2Gas to the saturated and tert-butyl alcohol that adds 1 ~ 2 mmol/L to remove the aqueous solution ionization hydroxyl radical free radical that radiolysis was produced; The oxidisability condition is to the logical N of carbon nano-tube aqueous solutions
2O gas ionizes the aqueous electron that radiolysis was produced to saturated to remove aqueous solution.
7. detect the photochemically reactive method of carbon nano-tube according to a kind of transient absorption spectroscopy that utilizes claimed in claim 1, it is characterized in that: the supernatant liquor to be detected of carbon nano-tube aqueous solutions also passes through Air Exposure among the described step a, and described Air Exposure is directly to carry out in the sample cell with the experimental apparatus of sealed membrane good seal.
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Cited By (4)
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CN105973942A (en) * | 2016-05-10 | 2016-09-28 | 国家纳米科学中心 | Synchronous electric regulation and control and material transient absorption spectrum measuring device and method |
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Cited By (7)
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CN105973942A (en) * | 2016-05-10 | 2016-09-28 | 国家纳米科学中心 | Synchronous electric regulation and control and material transient absorption spectrum measuring device and method |
CN105973942B (en) * | 2016-05-10 | 2019-01-25 | 国家纳米科学中心 | A kind of device and method of synchronous electricity regulation and material transient absorption spectrometry |
CN108088820A (en) * | 2017-12-14 | 2018-05-29 | 大连理工大学 | A kind of method that hydroxyl radical free radical is quantitatively detected using laser flash photolysis technology |
CN108088820B (en) * | 2017-12-14 | 2020-09-01 | 大连理工大学 | Method for quantitatively detecting hydroxyl free radicals by using laser flash photolysis technology |
CN109374595A (en) * | 2018-12-12 | 2019-02-22 | 中国科学技术大学 | A kind of detection system of ultrafast pulse radiolysis |
CN114166835A (en) * | 2021-12-08 | 2022-03-11 | 桂林医学院 | Method for analyzing drug content in health product by tracing auxiliary agent |
CN114166835B (en) * | 2021-12-08 | 2024-02-20 | 桂林医学院 | Method for analyzing drug content in health care product by tracing auxiliary agent |
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