CN110376261A - A kind of electrochemistry imaging system and method based on the adjustable light scatter properties of graphene - Google Patents
A kind of electrochemistry imaging system and method based on the adjustable light scatter properties of graphene Download PDFInfo
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- G01N2021/4797—Scattering, i.e. diffuse reflection spatially resolved investigating of object in scattering medium time resolved, e.g. analysis of ballistic photons
Abstract
The invention belongs to optical microphotograph instrument manufacturing technology and electrochemistry technical field of imaging, in particular to a kind of electrochemistry imaging system and method based on the adjustable light scatter properties of graphene, the system comprises graphene cell system, microscopic system, image-forming module and image processing modules；The graphene cell system is using graphene as working electrode；The microscopic system and image-forming module are arranged in the scattering light optical path of black alkene cell system；Described image processing module extracts the picture that image-forming module obtains, and by carrying out calculation process to picture scattered light intensity, obtains the picture for indicating target sample local surfaces faraday and nonfaradaic current density, realizes electrochemistry imaging；Electrochemistry imaging method based on the adjustable light scatter properties of graphene of the invention, the local surfaces electrochemical signals of multiple target samples in the visual field can be detected simultaneously by, the na level of the sensitivity for acquiring electric current from the prior art is made to drop to an angstrom peace grade by matched scatter imaging system, while spatial resolution significantly improves.
Description
Technical field
The invention belongs to optical microphotograph instrument manufacturing technology and electrochemistry technical field of imaging, in particular to a kind of to be based on stone
The electrochemistry imaging system and method for the black adjustable light scatter properties of alkene.
Background technique
Electrochemical analysis techniques are a kind of widely applied analysis means, can be used for detecting and understanding electrode surface
Electrochemical reaction, thus have received widespread attention.In order to obtain better detection sensitivity and spatial resolving power, researcher
Develop numerous electrochemistry microscopic image analysis methods, common two classes that are divided into: scan-type electrochemical microscope (SECM) and
Plasma electric chemical microscope (P-ECi).Scan-type electrochemical microscope is scanned sample surfaces by microelectrode, acquisition office
The current signal in portion.The small refractive index that plasma electric chemical microscope then passes through detection substance state before and after redox becomes
Change quick, the sensitive imaging realized to local current signal.Both the above electrochemistry micro-imaging technique is illustrated to small
The detection potentiality of electrochemical signals, but it is constrained to na level response sensitivity.Sensitivity is mainly by background dark current and non-electrical
The interference decision of chemical reaction.Other such as the methods of ultramicroelectrodes, Surface enhanced Raman scattering also fail to break through na level
Limitation.
Summary of the invention
The present invention solves the above-mentioned technical problems in the prior art, provides a kind of electrification of quick, highly sensitive response
It studies as system and method；Electrochemistry imaging method based on the adjustable light scatter properties of graphene of the invention, can detect simultaneously
The local surfaces electrochemical signals of multiple target samples into the visual field, acquire the na level of the sensitivity of electric current from the prior art
Angstrom peace (aA) grade is dropped to, while spatial resolution significantly improves.
To solve the above problems, technical scheme is as follows:
A kind of electrochemistry imaging system based on the adjustable light scatter properties of graphene, including it is graphene cell system, aobvious
Micromirror systems, image-forming module and image processing module；
The graphene cell system includes working electrode, to electrode, reference electrode and electrolyte solution, the work
Electrode is graphene；
The graphene cell system is connected with potential control instrument；
On the output light path for the light source that microscopic system is arranged in the graphene cell system and image-forming module；
The microscopic system and image-forming module are arranged in the scattering light optical path of black alkene cell system；
The scattered light intensity variation of working electrode in the image-forming module record graphene cell system；
Described image processing module extracts the picture that image-forming module obtains, by carrying out at operation to picture scattered light intensity
Reason obtains the local surfaces current density of target sample, realizes the imaging of time-space resolution electrochemistry.
Preferably, the working electrode is the graphene of single layer or few layer CVD growth；Graphene electrodes can also pass through other
Method obtains, such as vapor deposition, transfer, growth mode.
Preferably, described is platinum electrode to electrode, and reference electrode is silver/silver chloride electrode, and electrolyte solution is nitric acid
Potassium solution.Other inactive, conductive materials can also be used to replace at electrode；Reference electrode is replaced using calomel electrode etc.；Electrolyte is molten
Liquid can also select as needed, such as PBS solution (phosphate buffer solution), Klorvess Liquid.
Preferably, the image-forming module is scattered light imaging to working electrode in graphene cell system, and records
The scattered light intensity of each pixel changes.
Preferably, the nano particle conduct with plasma resonance scattering nature is added in the graphene cell system
Nano-electrode, such as gold, silver, Pt nanoparticle；It can play the role of amplified signal.
Preferably, the light source of the microscopic system is the width that a branch of wavelength is any wave band within the scope of 200 to 20000nm
Compose the laser light source of any wavelength within the scope of light source or 200 to 20000nm.
Preferably, the potential control instrument is electrochemical workstation or potentiostat；The electrochemical workstation connection
The working electrode of the graphene cell system, to electrode and reference electrode；The electrochemical workstation is applied to working electrode
Add electric potential signal of multiple waveforms, including triangular wave, sine wave, square wave etc., for generating electrochemical reaction；The electrochemistry work
The current signal for making station while collecting work electrode, for recording macroscopical electrochemical signals of the electrode.
Preferably, the image-forming module is CMOS camera, CCD camera or photomultiplier tube.
Preferably, the microscopic system is that total internal reflectance microscope, transmission-type dark field microscope, reflective dark field are micro-
Mirror, mating plate microscope, Laser Scanning Confocal Microscope, any one in endoscope；It is described when microscopic system is total internal reflectance microscope
Pulsed light beam passes through the oil mirror of high-NA, to be greater than 70 ° of high angle irradiating sample platform；It generates total internal reflection (TIR)；Benefit
The nano particle of the evanescent field irradiation graphene and its surface that are generated with TIR generates scattering, and the scattered light signal is by the oil mirror
Acquisition carries out dark field scattering imaging into the image-forming module.
Preferably, when electrochemical reactant is scattered in electrolyte solution, working electrode is applied using electrochemical workstation
Making alive, when potential reaches oxidation or the reduction potential of electrochemical reactant, electrochemical reactant diffuses to electrode surface simultaneously
Electronics transfer occurs, causes the variation of local graphite alkene surface charge, and then causes graphene scattered light intensity (nano particle is such as
Gold nano star can amplify scattered light intensity) variation (Δ I/I), the image-forming module records the variation of the scattered light intensity；Institute
The sequence of pictures 1 that image processing module obtains image-forming module is stated to generate by following relationship operation comprising current density information
The sequence of pictures 2 of i:
Wherein
Δ I/I indicates the change rate of the intensity value of each pixel of photo of sequence 1；
N indicates the single transfer electron number of surveyed electrochemical reaction；
E indicates elementary charge；
A indicates the ratio of carrier density and Δ I/I in graphene；
B=(zODO -1/2-zRDR -1/2)-1, the zOAnd zRRespectively indicate the oxidized and reduced of electrochemical reactant
Electrically charged, DOAnd DRRespectively indicate the diffusion coefficient of the oxidized and reduced of electrochemical reactant；
KaIndicate the adsorption equilibrium costant of surveyed electrochemical reactant；
L-1Indicate inverse Laplace's operation.
Preferably, when electrochemical reactant is adsorbed in working electrode surface, working electrode is applied using electrochemical workstation
Making alive, when potential reaches oxidation or the reduction potential of electrochemical reactant, electronics transfer occurs for electrochemical reactant, causes
The variation of local graphite alkene surface charge, and then cause graphene scattered light intensity (nano particle such as gold nano star can amplify scattered
Penetrate luminous intensity) variation (Δ I/I), the image-forming module records the variation of the scattered light intensity；Described image processing module will
The sequence of pictures 3 that image-forming module obtains generates the sequence of pictures 4 comprising current density information i by following relationship operation:
Wherein
A indicates the ratio of carrier density and Δ I/I in graphene；
E indicates elementary charge；
Δ I/I indicates the change rate of the intensity value of each pixel of photo of sequence 1；
T indicates the time.
Compared with the existing technology, advantages of the present invention is as follows,
Electrochemistry imaging system based on the adjustable light scatter properties of graphene of the invention is locally carried using graphene surface
The relationship for flowing sub- density and part scattering light property, by image processing module directly by the scattering particles of graphene and its surface
Scattered light intensity be converted to current data, the current density of multiple target samples in the visual field can be detected simultaneously by, it can be achieved that aA
The current detecting of rank limits.
The present invention is a kind of novel electrochemistry micro-imaging means, compared to current scan-type electrochemical microscope and is waited
Ion electrochemical microscopy has the raising of significant function and aspect of performance: based on the adjustable light scatter properties of graphene
The detection limit of the acquisition electric current of electrochemistry imaging system can be down to aA rank；The detection limit of more existing Naan has dropped 6 numbers
Magnitude.
Detailed description of the invention
Fig. 1 is the electrochemistry imaging system schematic diagram based on the adjustable light scatter properties of graphene of embodiment 1；In figure, 1 is
Graphene cell system, 11 be working electrode, and 12 be to electrode, and 13 be reference electrode, and 14 be electrolyte solution, and 2 be micro-
Mirror system, 3 are, 4 be image-forming module, and 5 be potential control instrument, and 100 be working electrode scattering light；
Fig. 2 is the scattering light image that working electrode surface deposits individual particle gold nano star；
Fig. 3 is single gold nano star charge and discharge cycles voltammogram in embodiment 2；
Fig. 4 a-d is Current density imaging figure under potentials different during potential scan in embodiment 3, when potential is -0.6V
When, gold nano star catalogue face has no apparent electric current, when potential is swept to 0.12V, has maximum oxidation current, then gradually disappears
It loses, reduction current occurs, reduction current reaches maximum value in 0.02V；E is cyclic voltammetry curve, 5 for choosing Fig. 4 a-d label
The analysis of gold nano star, discovery have the CV curve of standard；F is cyclic voltammetry curve, and the CV's of the background graphene of acquisition is averaged
Value and the macroscopical CV perfect matching obtained by electrochemical workstation, and the average value of the CV of the multiple gold nano stars obtained is obviously strong
In background graphene and macroscopic view CV；
Fig. 5 a is the transmission electron microscope picture for having modified the gold nano star of cytochrome c, gold nano star catalogue face be adsorbed with having a size of
The bump of 3-6nm, corresponding single or multiple cytochrome c molecules；Fig. 5 b is that potential is during cyclic voltammetric potential scan
Current density imaging figure when 0.16V, wherein there is more apparent oxidation peak current in gold nano star；Fig. 5 c is dissipating for the region
Penetrate image；Fig. 5 d is cyclic voltammetry curve, chooses No. 1 gold nano star and 6 for having modified cromoci indicated in Fig. 5 b-c
The gold nano star of number unmodified cytochrome c, calculates separately the CV curve for obtaining them, and compare in ideal CV curve.
Specific embodiment
Embodiment 1:
Such as Fig. 1, a kind of electrochemistry imaging system based on the adjustable light scatter properties of graphene, including graphene electrolytic cell system
System 1, microscopic system 2, image-forming module 3 and image processing module 4；
The graphene cell system 1 includes working electrode 11, to electrode 12, reference electrode 13 and electrolyte solution
14, the working electrode 11 is graphene；Specifically, graphene used by the present embodiment is single layer or few layer (3-5 layers) CVD
The graphene of growth, platinum filament are used as to electrode, silver/silver chlorate as reference electrode, and electrolyte solution is potassium nitrate solution；Its
In, Graphene electrodes can be obtained by other methods, such as vapor deposition, transfer, growth mode；Electrode and reference electrode can be used
Other conductive materials replace.
The graphene cell system 1 is connected with potential control instrument 5；Electrochemistry may be selected in the potential control instrument
Work station or potentiostat；In the present embodiment, the graphene cell system is connected with electrochemical workstation, the electrochemistry
Work station connects the working electrode of the graphene cell system, to electrode and reference electrode；The electrochemical workstation to
Working electrode applies the electric potential signal, including triangular wave, sine wave, square wave etc. of multiple waveforms, for generating electrochemical reaction；Institute
The current signal for stating electrochemical workstation while collecting work electrode, for recording macroscopical electrochemical signals of the electrode.
On the output light path for the light source that microscopic system 2 is arranged in the graphene cell system 1 and image-forming module 3.
The microscopic system 2 and image-forming module 3 are arranged in the scattering light optical path of black alkene cell system 1.
The image-forming module 3 records the scattered light intensity variation of working electrode 11 in graphene cell system 1；It is preferred that
Ground, the image-forming module 3 is scattered light imaging to working electrode 11 in graphene cell system 1, and records each pixel
The scattered light intensity variation of point.
The light source of the microscopic system 2 is the wide spectrum optical that a branch of wavelength is any wave band within the scope of 200 to 20000nm
The laser light source of any wavelength within the scope of source or 200 to 20000nm.
The microscopic system 2 is total internal reflectance microscope, transmission-type dark field microscope, reflective dark-field microscope, light
Piece microscope, Laser Scanning Confocal Microscope, any one in endoscope.When microscopic system is total internal reflectance microscope, the pulse
Light beam passes through the oil mirror of high-NA, to be greater than 70 ° of high angle irradiating sample platform；It generates total internal reflection (TIR)；It utilizes
The nano particle of evanescent field irradiation graphene and its surface that TIR is generated generates scattering, and 100 signal of scattering light is by the oil mirror
Acquisition carries out dark field scattering imaging into the image-forming module.
The image-forming module 3 is CMOS camera, CCD camera or photomultiplier tube.
Described image processing module 4 extracts the picture that image-forming module obtains, by carrying out operation to picture scattered light intensity
Processing obtains the local surfaces current density of target sample, realizes the imaging of time-space resolution electrochemistry.
For amplified signal, can also be added in the graphene cell system 1 with plasma resonance scattering nature
Nano particle is as nano-electrode, such as gold, silver, Pt nanoparticle；As shown in Fig. 2, the graphene cell system 1 of the present embodiment
Middle 11 surface of working electrode deposits the individual particle gold nano star that interior nuclear diameter is 80nm.
Embodiment 2:
With the electrochemistry imaging system described in embodiment 1 based on the adjustable light scatter properties of graphene, electrochemistry is utilized
Work station sweeps fast 0.1V/s to working electrode application, and range -0.3 arrives the triangular wave potential of 0.3V, carries out cyclic voltammetry scan.
Such as Fig. 3, described image processing module extracts the picture that image-forming module obtains, by carrying out to picture scattered light intensity
Calculation process obtains the current density of single gold nano star；
It as shown in the figure, is 7.18 × 10 by the noise of standard deviation calculation current density-4A m-2.The gold nano star
Near-field scattering section be 2.10 × 10-15m2.Therefore, by the three times signal-to-noise ratio of calculating current noise, the detection of electric current is limited to
4.52×10-18A, i.e. 4.52aA.
Based on above-mentioned experiment, the electrochemistry imaging system of the invention based on the adjustable light scatter properties of graphene can be used for examining
Survey the electric current on single gold nano star, detection limit is down to an angstrom peace rank, low 6 orders of magnitude of the detection limit of more current na level.
Embodiment 3:
With embodiment 2, the difference is that, the 1mM potassium ferricyanide is added in electrolyte, sweeps fast 0.1V/ to working electrode application
S, range -0.6 arrive the triangular wave potential of 0.6V, carry out cyclic voltammetry scan.
Described image processing module extract image-forming module obtain picture, by following formula to picture scattered light intensity into
Row calculation process, obtaining indicates target sample local current densities, realizes the imaging to the electrochemical reaction on single nanometer star
Analysis；
Meanwhile macroscopical cyclic voltammetry curve of the graphene cell system acquisition.
Such as Fig. 4 a-d, when potential is -0.6V, gold nano star catalogue face has no apparent electric current, when potential is swept to 0.12V
When, there is maximum oxidation current, then fade away, reduction current occur, reduction current reaches maximum value in 0.02V.
5 gold nano stars analysis of label is chosen, discovery has the CV curve of standard, such as Fig. 4 e, it will be apparent that redox
Peak corresponds to the redox of the potassium ferricyanide.Different peak heights is due to the difference in surface areas before different gold nano stars.It obtains
The average value of the CV of the background graphene obtained and the macroscopical CV perfect matching obtained by electrochemical workstation, and the multiple gold obtained
The average value of the CV of nanometer star is significantly stronger than background graphene and macroscopic view CV, such as Fig. 4 f.
Based on above-mentioned experiment, the electrochemistry imaging system of the invention based on the adjustable light scatter properties of graphene can be used for examining
Survey the redox reaction occurred on single gold nano star, the result of the current density numerical value of acquisition and commercial electrochemical workstation
Unanimously.
Embodiment 4:
With embodiment 2, the difference is that, gold nano star surface modification cell coloring matter C molecule.As shown in Figure 5 a
Electron microscope, gold nano star catalogue face is adsorbed with the bump having a size of 3-6nm, corresponding single or multiple cytochrome c molecules.It is right
Fast 0.1V/s is swept in working electrode application, and range -0.4 arrives the triangular wave potential of 0.5V, carries out cyclic voltammetry scan.
Described image processing module extract image-forming module obtain picture, by following formula to picture scattered light intensity into
Row calculation process, obtaining indicates target sample local current densities, realizes the imaging to the electrochemical reaction on single nanometer star
Analysis；Meanwhile macroscopical cyclic voltammetry curve of the graphene cell system acquisition
When potential scan is to 0.16V, there is more apparent oxidation in gold nano star in the Current density imaging in Fig. 5 b
Peak current.Choose the gold of No. 1 gold nano star for having modified cromoci and No. 6 unmodified cytochrome cs that indicate in Fig. 5 b-c
Nanometer star, calculates separately the CV curve for obtaining them, and compare in ideal CV curve, such as Fig. 5 d.Cromoci is modified
Gold nano star i there is the curve similar with ideal CV, and the gold nano star vi of unmodified cytochrome c then not any oxygen
Change reduction peak to occur.
Based on above-mentioned experiment, the electrochemistry imaging system of the invention based on the adjustable light scatter properties of graphene can be used for examining
Survey the cell coloring matter C molecule redox reaction of the unimolecule rank on single gold nano star, the current density numerical value of acquisition with
The result of ideal CV is consistent.
It should be noted that above-described embodiment is only presently preferred embodiments of the present invention, there is no for the purpose of limiting the invention
Protection scope, the equivalent substitution or substitution made on the basis of the above all belong to the scope of protection of the present invention.
Claims (10)
1. a kind of electrochemistry imaging system based on the adjustable light scatter properties of graphene, which is characterized in that be electrolysed including graphene
Cell system, microscopic system, image-forming module and image processing module；
The graphene cell system includes working electrode, to electrode, reference electrode and electrolyte solution, the working electrode
For graphene；
The graphene cell system is connected with potential control instrument；
On the output light path for the light source that microscopic system is arranged in the graphene cell system and image-forming module；
The microscopic system and image-forming module are arranged in the scattering light optical path of black alkene cell system；
The scattered light intensity variation of working electrode in the image-forming module record graphene cell system；
Described image processing module extracts the picture that image-forming module obtains, by carrying out calculation process to picture scattered light intensity,
The local surfaces current density of target sample is obtained, realizes the imaging of time-space resolution electrochemistry.
2. the electrochemistry imaging system as described in claim 1 based on the adjustable light scatter properties of graphene, which is characterized in that institute
State the graphene that working electrode is single layer or few layer CVD growth.
3. the electrochemistry imaging system as described in claim 1 based on the adjustable light scatter properties of graphene, which is characterized in that institute
Stating to electrode is platinum electrode, and reference electrode is silver/silver chloride electrode, and electrolyte solution is potassium nitrate solution.
4. the electrochemistry imaging system as described in claim 1 based on the adjustable light scatter properties of graphene, which is characterized in that institute
It states image-forming module and light imaging is scattered to working electrode in graphene cell system, and record the scattering light of each pixel
Strength Changes.
5. the electrochemistry imaging system as described in claim 1 based on the adjustable light scatter properties of graphene, which is characterized in that institute
Stating to be added in graphene cell system has the nano particle of plasma resonance scattering nature as nano-electrode.
6. the electrochemistry imaging system as described in claim 1 based on the adjustable light scatter properties of graphene, which is characterized in that institute
State microscopic system light source be a branch of wavelength be within the scope of 200 to 20000nm the wide spectrum light source of any wave band or 200 to
The laser light source of any wavelength within the scope of 20000nm.
7. the electrochemistry imaging system as described in claim 1 based on the adjustable light scatter properties of graphene, which is characterized in that institute
Stating potential control instrument is electrochemical workstation or potentiostat.
8. the electrochemistry imaging system as described in claim 1 based on the adjustable light scatter properties of graphene, which is characterized in that institute
Stating image-forming module is CMOS camera, CCD camera or photomultiplier tube；The microscopic system is total internal reflectance microscope, transmission
Formula dark field microscope, reflective dark-field microscope, mating plate microscope, Laser Scanning Confocal Microscope, any one in endoscope.
9. a kind of electrochemistry imaging method based on the adjustable light scatter properties of graphene, which comprises the following steps:
It disperses electrochemical reactant in electrolyte solution described in claim 1, using potential control instrument to work
To make electrode and applies voltage, the image-forming module record causes the variation (Δ I/I) of the working electrode graphene scattered light intensity,
The sequence of pictures 1 that described image processing module obtains image-forming module is generated by following relationship operation to be believed comprising current density
Cease the sequence of pictures 2 of i:
Wherein
Δ I/I indicates the change rate of the intensity value of each pixel of photo of sequence 1；
N indicates the single transfer electron number of surveyed electrochemical reaction；
E indicates elementary charge；
A indicates the ratio of carrier density and Δ I/I in graphene；
B=(zODO -1/2-zRDR -1/2)-1, the zOAnd zRRespectively indicate being charged for the oxidized and reduced of electrochemical reactant
Lotus, DOAnd DRRespectively indicate the diffusion coefficient of the oxidized and reduced of electrochemical reactant；
KaIndicate the adsorption equilibrium costant of surveyed electrochemical reactant；
L-1Indicate inverse Laplace's operation.
10. a kind of electrochemistry imaging method based on the adjustable light scatter properties of graphene, which comprises the following steps:
Electrochemical reactant is adsorbed in working electrode surface described in claim 1, using potential control instrument to work
To make electrode and applies voltage, the image-forming module record causes the variation (Δ I/I) of the working electrode graphene scattered light intensity,
The sequence of pictures 3 that described image processing module obtains image-forming module is generated by following relationship operation to be believed comprising current density
Cease the sequence of pictures 4 of i:
Wherein
A indicates the ratio of carrier density and Δ I/I in graphene；
E indicates elementary charge；
Δ I/I indicates the change rate of the intensity value of each pixel of photo of sequence 1；
T indicates the time.
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