CN111318274B - Single-particle photocatalytic material, single-molecule fluorescence detection method, single-molecule fluorescence detection device and application - Google Patents
Single-particle photocatalytic material, single-molecule fluorescence detection method, single-molecule fluorescence detection device and application Download PDFInfo
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Abstract
The invention relates to the technical field of single-molecule fluorescence detection, in particular to a single-particle photocatalytic material, a single-molecule fluorescence detection method, a single-molecule fluorescence detection device and application thereof. The invention constructs single-particle TiO by 2 The carbon nanotube-loaded catalytic reaction system is used for analyzing the photoinduced electron transmission process on the surface of the single-particle catalyst in real time and in situ visualization on a single-molecule level. The invention successfully constructs an in-situ and visual detection model of single-particle catalyst surface photoinduced electron transmission based on a microfluidic chip and a total internal reflection fluorescence microscope device system. Analyzing the generation and transmission rate of photoinduced electrons from a time scale through the collected monomolecular fluorescence signals; further researching the influence of heterogeneous structure and defect effect on the electron transmission process, establishing structure-activity relationship between the catalyst structure and photoinduced electron transmission behavior, providing a new idea for deeply exploring the catalytic reaction mechanism and providing a new method for guiding and designing high-efficiency catalysts.
Description
Technical Field
The invention relates to the technical field of single-molecule fluorescence detection, in particular to a single-particle photocatalytic material, a single-molecule fluorescence detection method, a single-molecule fluorescence detection device and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The basic process of the photocatalytic reaction comprises: photoexcited electron-hole pair separation, photoinduced electron and hole transfer to the surface of the catalyst particles and initiation of redox reactions at the catalyst surface. The generation, separation and transmission behaviors of photo-induced electrons are closely related to the structural composition of the catalyst, and are key factors for determining the efficiency of catalytic reaction. In recent years, a research hotspot is to design and synthesize a catalyst with high-efficiency mass-charge separation capacity based on the modes of regulating the size and the specific surface area of catalyst particles, constructing a heterogeneous structure, doping metal or non-metal impurities, enriching active sites of the catalyst and the like, so as to improve the photocatalytic reaction performance. However, the intrinsic factors such as the size, defects and heterojunction of the existing catalyst and the external factors such as illumination, flow rate and solution concentration have no clear influence mechanism on the generation, transmission, recombination and distribution of photoelectrons in the photocatalytic reaction system. Therefore, the research on the transmission path of photoinduced electrons in the photocatalytic reaction process and the analysis of key factors influencing photoinduced electron transmission have important significance for deeply understanding the photocatalytic reaction mechanism, guiding the design and synthesis of a novel photocatalyst and representing a novel photocatalytic process.
Because photoinduced electrons generated on the surface of catalyst particles have the characteristics of high activity, low content, short service life and the like, accurate quantitative analysis of the photoinduced electrons is a difficult point for research. The traditional detection method is mainly based on the macroscopic level analysis of electron transport kinetics, such as Transient Absorption Spectroscopy (TAS), transient Photocurrent (TPC), photoluminescence spectroscopy (PL), transient Surface Photovoltage (TSPV), electrochemical Impedance (EIS), and the like, that is, the electron transport behavior of the catalyst particles is characterized integrally by electrochemical and spectroscopic techniques. However, the total response signal obtained by the macroscopic detection method can cover the complexity of the form, composition and structure of the single-particle catalyst, neglecting the heterogeneity (defect effect, heterojunction effect, crystal face effect and the like) of the catalyst, and greatly limits further understanding of the photoinduced electron transmission rate and transmission range of the surface of the single-particle catalyst. Therefore, in order to deeply understand the structure-activity relationship between the photoinduced electron transport process and the intrinsic characteristics of the catalyst and environmental factors and to explain the transport kinetics of photoinduced electrons in detail, it is very necessary to study the photoinduced electron transport behavior based on the single particle level.
The single molecule/single particle fluorescence imaging technology has the advantages of high detection sensitivity, high space-time resolution, individual behavior difference visualized analysis and the like, and is widely applied to the research fields of single molecule biological detection, drug tracing, single particle nano catalysis and the like. The single molecule/single particle fluorescence detection method realizes real-time in-situ imaging of a catalytic reaction system from macro to micro and from whole to individual. Researchers expound the distribution difference of the surface active sites of a single nano catalyst by using a single molecule/single particle fluorescence detection method; various catalytic behaviors and dynamic processes on the surface of the single nanoparticle are analyzed; the active oxygen species at the surface of the single catalyst particles were detected.
Disclosure of Invention
The problems solved by the invention are as follows: the existing single molecule/single particle fluorescence detection method does not realize the real-time in-situ sensing of photoinduced electrons on the surface of catalyst particles, and is still inconvenient for accurately analyzing the generation, transfer and transmission processes of photoinduced electrons on the surface of the catalyst, deeply understanding a photocatalytic reaction mechanism and guiding the design of a high-efficiency catalyst. Therefore, it is urgently needed to establish an in-situ detection method with high flux, high sensitivity and high spatial resolution, which is used for researching the photoinduced electron transfer process on the surface of the single-particle catalyst. Therefore, the invention provides a single-particle photocatalytic material, a single-molecule fluorescence detection method, a detection device and application thereof, which can realize the rapid, high-sensitivity and high-resolution detection of photoinduced electron transmission behaviors and can quantify the photoinduced electron transmission rate and the transmission range.
In order to achieve the above purpose, the invention specifically discloses the following technical scheme:
in a first aspect of the invention, a single particle photocatalytic material is disclosed, which is made of single particle TiO 2 Formed on multi-walled carbon nanotubes (MWCNTs).
Further, the single-particle photocatalytic material refers to a single MWCNT concentrated with TiO at a certain position 2 And TiO 2 2 And a heterojunction is formed between the MWCNTs.
Further, the preparation method of the single-particle photocatalytic material comprises the following steps:
(1) Mixing MWCNT and TiO 2 Respectively adding into solvent to obtain MWCNT dispersion solution and TiO 2 A dispersion liquid;
(2) Adding TiO into the mixture 2 The dispersion is added to the MWCNT dispersionUltrasonic treatment is carried out, the obtained mixed solution is dried under the empty condition, and then the obtained solid product is calcined, thereby the granular TiO is treated 2 Loaded onto MWCNTs to form a single particle photocatalytic material.
Further, in the step (1), the preparation method of the dispersion liquid comprises the following steps: mixing MWCNT and TiO 2 Respectively placing in a container, adding ethanol solution for dispersing and dissolving, sealing the container with a sealing film to prevent ethanol volatilization, and performing ultrasonic treatment to obtain black MWCNT dispersion and TiO 2 And (3) dispersing the mixture.
Further, in the step (2), the TiO in the mixed solution 2 And the MWCNT mass ratio of 900-1050:1; preferably, the ratio of 1000:1.
further, in the step (2), the calcining temperature is 300-380 ℃ and the time is 4.5-6h.
In a second aspect of the invention, the application of the single-particle photocatalytic material in the research of photoinduced electron transport detection on the surface of catalyst particles is disclosed.
Further, the application is to load single-particle TiO 2 The MWCNT is used as a catalyst, ultraviolet light is adopted to irradiate the MWCNT so as to excite photoinduced electron-hole pair separation on the surface of the catalyst, and then a monomolecular fluorescence image and a monomolecular fluorescence signal are collected for research.
Due to TiO 2 The MWCNT is a semiconductor photocatalyst with high catalytic activity and chemical stability, is the most typical one-dimensional nano material, and has good mechanical, electrical and chemical properties. Single particle TiO 2 The catalytic reaction system formed by the loaded MWCNT can promote effective separation of mass and charge, so that photoinduced electrons generated in the catalytic process can be quickly transferred to the MWCNT, the recombination time of the photoinduced electrons and holes is prolonged, the electronic transfer capability and the photocatalytic reaction efficiency are better, and the real-time and in-situ visual analysis of the photoinduced electron transmission process on the surface of the single-particle catalyst on the single-molecule level is realized.
In a third aspect of the present invention, a single-molecule fluorescence detection device is disclosed, which comprises the following components: the device comprises a micro-fluidic chip, a catalytic light source, a total internal reflection fluorescence microscope light path system, a dichroic mirror, a filter, an EMCCD (electron-multiplying charge coupled device) and an imaging system. The micro-fluidic chip is internally provided with a reaction tank, the reaction tank is composed of two glass sheets and two double-sided adhesive tapes, the double-sided adhesive tapes are adhered between the two transparent glass sheets, the two double-sided adhesive tapes are arranged at intervals, so that the reaction tank is formed, and the photocatalytic reaction is carried out in the reaction tank. The catalytic light source and the total internal reflection fluorescence microscope light path system are respectively used for providing catalytic light and laser with single wavelength for the reaction tank. The dichroic mirror is used for collecting fluorescence signals excited in the reaction tank, and the dichroic mirror, the filter, the EMCCD and the imaging system are sequentially connected.
In a fourth aspect of the present invention, a single-molecule fluorescence detection method is disclosed, comprising the following steps:
(1) The photocatalytic reaction is carried out in the reaction tank, the reaction solution containing the single-particle photocatalytic material passes through the reaction tank, and a catalytic light source with a single wavelength is applied to promote TiO 2 And (3) separating photoinduced electrons from holes, and quickly transferring the photoinduced electrons onto the MWCNT to contact with a solution system to generate OH active oxygen species which are specifically recognized by HPF, so as to generate a fluorescent product.
(2) Then, incident laser is applied through a total internal reflection fluorescence microscope optical path system, evanescent waves are generated on the glass sheet through total internal reflection, fluorescent molecules in a region close to the total internal reflection are excited, fluorescent signals emitted by the fluorescent molecules are collected in a dichroic mirror, single-molecule fluorescence is captured through a high-sensitivity EMCCD, and a single-molecule fluorescence image is obtained through computer imaging processing.
(3) And then preprocessing the obtained single-molecule fluorescence image through low-pass filtering so as to reduce the interference of baseline fluctuation on a fluorescence signal in the acquisition process and calibrate the single-molecule fluorescence intensity burst baseline. By setting a fluorescence intensity threshold, the influence of background fluorescence signals is eliminated, and effective single-molecule fluorescence signals are successfully obtained. The collected single-molecule fluorescence signal is then used for single-particle surface photo-induced electron transfer rate calculation.
The single-particle photocatalytic material can successfully realize rapid, high-sensitivity and high-resolution detectionThe reason for the photo-induced electron transport behavior is: tiO 2 2 After photo-induced electron-hole separation, photo-induced electrons are separated from the TiO 2 The surface diffuses along the MWCNT, gradually decreasing in electron density from core burst to the end of the MWCNT. However, due to the existence of defect effect, heterogeneity effect and lattice plane effect, the phenomena of accumulation, attenuation, quenching and the like of fluorescence signals on the MWCNT occur, and the influence of intrinsic factors (morphology, defects, heterojunction and the like) of the material on the transmission behavior of the photoelectrons is indirectly reflected.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention constructs a photocatalytic reaction system with high-efficiency mass-charge separation capability, is used for photoinduced electron transmission detection on the surface of catalyst particles, can quickly transfer photoinduced electrons generated in the catalysis process to MWCNT, prolongs the recombination time of the photoinduced electrons and holes, and has better electron transfer capability and photocatalytic reaction efficiency.
(2) The invention provides a real-time in-situ visualized single-molecule fluorescence detection method for detecting the surface photoinduced electron transmission rate of a single-particle catalyst, and the method provides a new thought for further understanding the structure-activity relationship between the complex structure of a catalyst material and a carrier transmission mechanism, accurately regulating and controlling the structure of the single-particle catalyst and designing a novel and efficient catalytic material.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a representation of MWCNT and single particle photocatalytic material of a first embodiment of the present invention; wherein: panel A is a Scanning Electron Micrograph (SEM) of pristine MWCNT; FIG. B is a Transmission Electron Micrograph (TEM) of pristine MWCNT; c is a scanning electron microscope image of the single-particle photocatalytic material; d is a transmission electron microscope image of the single-particle photocatalytic material; e-plot is elemental analysis plot (Mapping) of pristine MWCNTs; and the F picture is an element analysis picture of the single-particle photocatalytic material.
FIG. 2 is a schematic structural diagram of a monomolecular fluorescence detecting apparatus according to a fourth embodiment of the present invention; the scores in the figure represent: 1-microfluidic chip, 2-catalytic light source, 3-total internal reflection fluorescence microscope light path system, 4-dichroic mirror, 5-filter, 6-EMCCD, and 7-imaging system.
Fig. 3 is a schematic diagram of the principle of the single-particle photocatalytic material of the present invention for analyzing the photo-induced electron transport process on the surface of the single-particle catalyst.
FIG. 4 is a diagram showing a feasibility analysis of a fluorescent probe according to a fifth embodiment of the present invention; wherein: a is hydroxyl radical (. OH) of a hydroxyphenyl fluorescein (HPF) specific fluorescent probe detection solution system; graph B shows the OH response curves generated by HPF for different materials.
FIG. 5 is a graph showing the processing of a single-molecule fluorescent signal in a sixth embodiment of the present invention; wherein: a is a comparison chart before and after background signal calibration; and B is a comparison chart before and after single-molecule fluorescence signal calibration.
FIG. 6 is a graph showing the photo-induced electron transport rate on the surface of a single-particle catalyst in a seventh example of the present invention; wherein: a is derived from TiO 2 A graph of the transmission rate of photoinduced electrons from the core explosion point region to the end of the MWCNT; and B is a diagram of the photo-induced electron transmission decay rate in different areas.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As described above, the existing single-molecule/single-particle fluorescence detection method does not realize real-time in-situ sensing of photo-induced electrons on the surface of catalyst particles, and it is still inconvenient to accurately analyze the generation, transfer and transmission processes of photo-induced electrons on the surface of catalyst, deeply understand the photo-catalytic reaction mechanism, and guide the design of high-efficiency catalyst. Therefore, the invention provides a single-particle photocatalytic material, a single-molecule fluorescence detection method, a single-molecule fluorescence detection device and application thereof, and the invention is further explained by combining the attached drawings and the specific embodiment.
First embodiment
A preparation method of a single-particle photocatalytic material comprises the following steps:
(1) About 1g MWCNT and 0.01g TiO were weighed 2 Respectively placing in 50mL beaker, adding 10mL ethanol solution respectively, dispersing and dissolving, ultrasonic processing for 2h (sealing the beaker with sealing film to prevent ethanol volatilization), the MWCNT dispersion is black, tiO 2 The dispersion did not change significantly.
(2) Remove 1mL of TiO with pipette 2 The dispersion was added to the MWCNT dispersion and sonication continued for 1h. Then pouring the mixed liquid after ultrasonic treatment into a 20mL porcelain crucible, firstly putting the crucible into a vacuum drying oven at 80 ℃ for drying, finally moving the crucible to a muffle furnace, calcining at 350 ℃ for 5 hours, and calcining the granular TiO in a high-temperature calcining manner 2 Loaded on MWCNT, on TiO 2 Forming a heterogeneous structure with MWCNT, namely obtaining the single-particle photocatalytic material.
The single-particle photocatalytic material prepared in this example was characterized and the results are shown in fig. 1, in which:
the A and B images are SEM and TEM images of the original MWCNT, respectively, from which it can be seen that no other material is loaded on the MWCNT.
Fig. C and D are SEM and TEM images, respectively, of the single-particle photocatalytic material prepared in this example, from which it can be seen that other materials of single particles were successfully supported on MWCNTs.
Panels E and F are elemental analysis diagrams of the pristine MWCNT and single particle photocatalytic materials, respectively. The results show that for unbound TiO 2 The MWCNT material of (1), the element C was concentrated on the MWCNT, and the element Ti and the element O were not detected; for binding TiO 2 Of MWCNT of (1)In the material, the element C was still concentrated in the MWCNT, and the element Ti and the element O were detected on a single particle, and the element C was not detected. This further verifies that the present invention successfully prepares single particle TiO 2 A single particle photocatalytic material formed on the MWCNT.
Second embodiment
A preparation method of a single-particle photocatalytic material comprises the following steps:
(1) About 0.9g of MWCNT and 0.01g of TiO were weighed 2 Respectively placing in 50mL beaker, adding 10mL ethanol solution, dispersing and dissolving, ultrasonic treating for 2 hr (sealing the beaker with sealing film to prevent ethanol volatilization), wherein MWCNT dispersion liquid is black ink, tiO 2 The dispersion did not change significantly.
(2) Remove 1mL of TiO with pipette 2 The dispersion was added to the MWCNT dispersion and sonication continued for 1h. Then pouring the mixed liquid after ultrasonic treatment into a 20mL porcelain crucible, firstly putting the crucible into a vacuum drying oven at 75 ℃ for drying, finally moving the crucible to a muffle furnace, calcining at 300 ℃ for 6h, and calcining the granular TiO in a high-temperature calcining manner 2 Loaded on MWCNT, on TiO 2 Forming a heterogeneous structure with MWCNT, namely obtaining the single-particle photocatalytic material.
Third embodiment
A preparation method of a single-particle photocatalytic material comprises the following steps:
(1) About 1.05g of MWCNT and 0.01g of TiO were weighed 2 Respectively placing in 50mL beaker, adding 10mL ethanol solution respectively, dispersing and dissolving, ultrasonic processing for 2h (sealing the beaker with sealing film to prevent ethanol volatilization), the MWCNT dispersion is black, tiO 2 The dispersion did not change significantly.
(2) Remove 1mL of TiO with pipette 2 The dispersion was added to the MWCNT dispersion and sonication continued for 1h. Then pouring the mixed liquid after ultrasonic treatment into a 20mL porcelain crucible, firstly putting the crucible in a vacuum drying oven at 80 ℃ for drying, finally moving the crucible to a muffle furnace, calcining at 380 ℃ for 4.5h, and calcining the granular TiO in a high-temperature calcining manner 2 Loaded on MWCNTs on TiO 2 And MWCNTForming a heterogeneous structure to obtain the single-particle photocatalytic material.
Fourth embodiment
A single molecule fluorescence detection device, as shown in fig. 2, comprising the following components: the device comprises a micro-fluidic chip 1, a catalytic light source 2, a total internal reflection fluorescence microscope light path system 3, a dichroic mirror 4, a filter 5, an EMCCD6 and an imaging system 7.
The micro-fluidic chip 1 is provided with a reaction tank, the reaction tank is composed of two glass sheets and two double-sided adhesive tapes, the double-sided adhesive tapes are adhered between the two transparent glass sheets, the two double-sided adhesive tapes are arranged at intervals, so that the reaction tank is formed, and the photocatalytic reaction is carried out in the reaction tank.
The catalytic light source 2 is used for providing catalytic light with a single wavelength into the reaction tank to promote TiO 2 Photoinduced electrons are separated from holes, and the photoinduced electrons are rapidly transferred to the MWCNT to be contacted with a solution system, so that OH active oxygen species specifically recognized by HPF are generated, and a fluorescent product is generated.
The total internal reflection fluorescence microscope optical path system 3 is used for providing incident laser for the reaction tank, and the laser total internal reflection generates evanescent waves on the glass sheet to excite fluorescent molecules in the area close to the total internal reflection.
The dichroic mirror 4 is used for collecting fluorescence signals excited in the reaction tank, the dichroic mirror 4, the filter 5, the EMCCD6 and the imaging system 7 are sequentially connected, the EMCCD is used for capturing single-molecule fluorescence, and the imaging system 7 is used for processing the captured single-molecule fluorescence to form a single-molecule fluorescence image.
Fifth embodiment
A single-molecule fluorescence detection method using the single-molecule fluorescence detection apparatus according to the second embodiment, comprising the steps of:
(1) The photocatalytic reaction was carried out in the reaction tank, and the reaction solution (flow rate 50. Mu. Lmin) containing the single-particle photocatalytic material prepared in the first example was supplied -1 ) TiO is promoted by passing through a reaction tank (glass sheet with length of 2cm, width of 0.5cm and height of 150 μm) and simultaneously applying a catalytic light source with a single wavelength of 365nm 2 And (3) separating photoinduced electrons from holes, and quickly transferring the photoinduced electrons onto the MWCNT to contact with a solution system to generate OH active oxygen species which are specifically recognized by HPF, so as to generate a fluorescent product.
(2) Then, incident laser with the wavelength of 488nm is applied through a total internal reflection fluorescence microscope light path system, evanescent waves (the thickness is about 200 nm) are generated on a glass sheet through total internal reflection, fluorescent molecules close to the total internal reflection area are excited, fluorescent signals emitted by the fluorescent molecules are collected in an eyepiece (100 xNA 1.4) of a dichroic mirror, single-molecule fluorescence is captured by using a high-sensitivity EMCCD, and finally, a fluorescence intensity-time curve graph of the single-molecule fluorescent signals is obtained through metaMorph microscope automation and imaging analysis software processing.
Feasibility analysis of fluorescent probes: as shown in fig. 3, the principle of the single-particle photocatalytic material of the present invention for analyzing the photoinduced electron transport process on the surface of the single-particle catalyst is as follows: the photo-excited single-particle catalyst has surface photoinduced electron-hole pair separation, and photoinduced electrons are transmitted to the MWCNT after mass-charge separation and are contacted with a solution system to generate OH active oxygen species.
Further, in this embodiment, a HPF-specific fluorescent probe is selected to detect the · OH of the solution system, and a response curve of the HPF fluorescent probe to the · OH within 0-40min of illumination time is analyzed by fluorescence spectroscopy, as shown in fig. 4A, the · OH concentration in the catalytic reaction system is accumulated as the illumination time increases, so that the fluorescence intensity and the illumination time show a positive correlation trend.
Meanwhile, this example sets up a control experiment to analyze TiO 2 The results of the response of the HPF fluorescent probe, the response of the MWCNT to the HPF fluorescent probe under the illumination condition, and the autocatalytic response of the HPF fluorescent probe under the illumination condition are shown in fig. 4B. As can be seen, MWCNT and HPF fluorescent probe alone hardly undergo catalytic reaction under light irradiation condition, MWCNT-doped TiO 2 Catalytic activity is higher than that of pure TiO 2 The catalytic activity of the compound is high, which indicates that the heterogeneous structure is more beneficial to the quick transfer of photoinduced electrons and improves the activity of photocatalytic reaction. Therefore, the fluorescence signal of OH can be detected based on the HPF fluorescent probe, and the carrier transmission behavior of the single-particle catalytic process can be indirectly reflected.
Sixth embodiment
Detecting and processing a single-molecule fluorescence signal: the fluorescence intensity-time curve obtained in the fifth embodiment is preprocessed by low-pass filtering, and then the signal diagram is preprocessed by low-pass filtering, so that the interference of baseline fluctuation in the acquisition process on the fluorescence signal is reduced, and the single-molecule fluorescence intensity explosion baseline is calibrated. By setting a fluorescence intensity threshold (threshold = average background fluorescence signal +3 σ, σ is standard deviation), the influence of the background fluorescence signal is eliminated, and an effective single-molecule fluorescence signal is successfully obtained. The collected single-molecule fluorescence signal is then used for calculating the single-particle surface photoelectron transmission rate, and the result is shown in fig. 5, wherein fig. 5A is a comparison graph before and after calibration of the background signal, fig. 5B is a comparison graph before and after calibration of the fluorescence signal, and the fluctuation amplitude of the calibrated signal is reduced. The blue line in the figure is the demarcated threshold line and it can be seen that the background fluorescence signal interference is reduced after signal calibration. This illustrates the successful acquisition of a single-molecule fluorescence signal by the single-molecule fluorescence detection device.
Seventh embodiment
And (3) detecting the photoinduced electron transmission rate of the surface of the single-particle catalyst: based on the monomolecular fluorescence signals obtained in the sixth example, the mean τ in the monomolecular fluorescence intensity-time series chart in the fourth example was counted off The method specifically comprises the following steps:
counting tau of fluorescence burst from the core burst area to the boundary area by using the processed single-molecule fluorescence intensity-time sequence chart off Time of day. Based on a rate formula
The fluorescence burst rates, i.e. the electron transport rates along the MWCNT, were calculated for different positions and the results are shown in fig. 6A. It can be seen that: from TiO 2 From the core explosion point area to the tail end of the MWCNT, the whole trend of the electron transmission rate is gradually reduced, and the electron transmission rate is from 17.03s -1 Decaying to 0.28s -1 . Although the overall trend of electron transport rate is decreasing, the degree of attenuation at different locations also varies, as shown in FIG. 6BThe maximum of the electron decay rate is shown to occur in the heterojunction region, indicating that there is a structure-activity relationship between the heterogeneity of the catalyst material and the photoinduced electron transport mechanism. Based on the constructed in-situ visual detection model of the surface carrier transmission of the single-particle catalyst with high sensitivity and high spatial resolution, a new thought is provided for further understanding a photoinduced electron transmission mechanism, accurately regulating and controlling the structure of the single-particle catalyst and designing a novel efficient catalytic material.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The application of single-particle photocatalytic material in the detection research of photoinduced electron transmission on the surface of catalyst particles is characterized in that single-particle TiO is loaded 2 The MWCNT is used as a catalyst, ultraviolet light is adopted to irradiate the MWCNT so as to excite the separation of photoinduced electron-hole pairs on the surface of the catalyst, and then a single-molecule fluorescence image and a single-molecule fluorescence signal are collected for research; the single-particle photocatalytic material is made of single-particle TiO 2 Formed supported on MWCNTs; the single-particle photocatalytic material is formed by combining TiO on a single MWCNT in a centralized way at a certain position 2 And TiO 2 2 And a heterojunction is formed between the MWCNTs.
2. The application of the single-particle photocatalytic material as claimed in claim 1 in the detection research of photoinduced electron transmission on the surface of catalyst particles, wherein the preparation method of the single-particle photocatalytic material comprises the following steps:
mixing MWCNT and TiO 2 Respectively adding into solvent to obtain MWCNT dispersion solution and TiO 2 A dispersion liquid;
adding TiO into the mixture 2 Adding the dispersion into MWCNT dispersion for ultrasonic treatment, drying the obtained mixed solution under vacuum condition, and calcining the obtained solid product to obtain particles TiO 2 Loaded onto MWCNTs to form a single particle photocatalytic material.
3. The application of the single-particle photocatalytic material as claimed in claim 2 in the detection research of photo-induced electron transport on the surface of catalyst particles, wherein the preparation method of the dispersion liquid comprises the following steps: mixing MWCNT and TiO 2 Respectively placing in a container, adding ethanol solution for dispersing and dissolving, sealing the container with a sealing film, and performing ultrasonic treatment to obtain black MWCNT dispersion and TiO 2 And (3) dispersing the mixture.
4. The use of the single-particle photocatalytic material of claim 2 in the detection of photo-induced electron transport on the surface of a catalyst particle, wherein the TiO is present in the mixture 2 And the MWCNT mass ratio of 900-1050:1.
5. the application of the single-particle photocatalytic material in the research of photo-induced electron transport detection on the surface of catalyst particles as claimed in claim 2, wherein the calcination temperature is 300-380 ℃ and the calcination time is 4.5-6h.
6. A single-molecule fluorescence detection method is characterized by being executed by a single-molecule fluorescence detection device and comprising the following steps:
the reaction liquid containing single-particle photocatalytic material passes through a reaction tank, and a catalytic light source with single wavelength is applied to promote TiO 2 Photo-induced electron and hole separation; photoinduced electrons are quickly transferred onto the MWCNT to contact with a solution system to generate OH active oxygen species which are specifically identified by HPF to generate a fluorescent product; then 488nm incident laser is applied through a total internal reflection fluorescence microscope light path system, so that the total internal reflection generates evanescent waves on the glass sheet, and fluorescent molecules in a region close to the total internal reflection are excited; collecting fluorescent signals emitted by fluorescent molecules in a dichroic mirror, capturing monomolecular fluorescence by using a high-sensitivity EMCCD (electron-multiplying charge coupled device), and performing computer development processing to obtain a monomolecular fluorescence image; subsequently preprocessing the obtained list by low-pass filteringA molecular fluorescence image; then eliminating the influence of background fluorescence signals by setting a fluorescence intensity threshold value to successfully obtain effective monomolecular fluorescence signals; then, the collected single-molecule fluorescence signal is used for calculating the photoinduced electron transmission rate on the surface of the single particle;
the single-molecule fluorescence detection device comprises the following components: the device comprises a micro-fluidic chip, a catalytic light source, a total internal reflection fluorescence microscope light path system, a dichroic mirror, a filter, an EMCCD (electron-multiplying charge coupled device) and an imaging system; the microfluidic chip is internally provided with a reaction tank, the reaction tank is composed of two glass sheets and two double-sided adhesive tapes, the double-sided adhesive tapes are adhered between the two transparent glass sheets, and the two double-sided adhesive tapes are arranged at intervals, so that the reaction tank is formed; the catalytic light source and the total internal reflection fluorescence microscope optical path system are respectively used for providing catalytic light and laser with single wavelength to the reaction tank; the dichroic mirror is used for collecting fluorescence signals excited in the reaction tank, and the dichroic mirror, the filter, the EMCCD and the imaging system are sequentially connected;
the single-particle photocatalytic material is made of single-particle TiO 2 Formed supported on MWCNTs;
the single-particle photocatalytic material is formed by combining TiO intensively at a certain position on a single MWCNT 2 And TiO 2 2 And a heterojunction is formed between the MWCNTs.
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| JP2008203172A (en) * | 2007-02-22 | 2008-09-04 | Fujifilm Corp | Surface plasmon enhanced fluorescence detection method |
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