CN103852502B - A kind of electrolytic cell and detection method being applicable to Tip-Enhanced Raman Spectroscopy technology - Google Patents
A kind of electrolytic cell and detection method being applicable to Tip-Enhanced Raman Spectroscopy technology Download PDFInfo
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- CN103852502B CN103852502B CN201410123332.9A CN201410123332A CN103852502B CN 103852502 B CN103852502 B CN 103852502B CN 201410123332 A CN201410123332 A CN 201410123332A CN 103852502 B CN103852502 B CN 103852502B
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
Abstract
The present invention relates to a kind of electrolytic cell and the detection method that are applicable to Tip-Enhanced Raman Spectroscopy technology, electrolytic cell possess structure simple, assemble the advantages such as quick.Critical piece comprises: electrolytic tank body, contrast electrode, to electrode, working electrode, optics window.Be open design above electrolytic cell, for the inserting needle of TERS needle point and scanning imagery provide sufficient space; Electrolytic cell side direction has otch, and optics window is pasted at this place; Laser incidence and Raman signal collection are all realized by same object lens, and optical axis is vertical with optics window; Working electrode tilts to install towards optics window in electrolytic cell, reduces the stop to light, improves launching efficiency and Raman signal intensity.TERS can be applied to electrochemical research by this electrolytic cell.
Description
Technical field
The present invention relates to a kind of spectroelectrochemistry electrolytic cell, particularly a kind of electrolytic cell being applicable to Tip-Enhanced Raman Spectroscopy technology, belong to galvanochemistry, spectroelectrochemistry field.
Background technology
Conventional electrochemical technology based on electrical signal detection can study burn into metal electrodeposition, electro-catalysis, molecule in significant process such as electrode surface absorption and reactions, obtains important application in the field such as material, the energy.But electrochemical techniques are difficult to the information obtaining molecular structure aspect from molecular level, which greatly limits its development.The spectroelectrochemistry technology being representative with galvanochemistry-infrared spectrum, galvanochemistry-Surface enhanced raman spectroscopy (EC-SERS) provides the finger print information of molecular structure aspect by molecular vibration spectrum, effectively compensate for the deficiency that galvanochemistry self exists.Particularly EC-SERS, raman spectral signal is very little by the interference of water, and the humidification of substrate greatly improves sensitivity.
But above-mentioned spectroelectrochemistry technology still exists wretched insufficiency, because they are all adopt light as exciting and detection signal, by the restriction of optical diffraction limit, the spatial resolution of its spectral signal cannot break through diffraction limit.For EC-SERS, spatial resolution is the highest can only reach sub-micrometer scale, and the spatial resolution of galvanochemistry-infrared spectrum is poorer.Rise along with the research such as nano electro-catalytic, unimolecule electro-catalysis is a large amount of at present, a kind of spectroelectrochemistry technology with nanometer scale spatial discrimination of active demand.
Tip-Enhanced Raman Spectroscopy technology (TERS) is the coupling of scanning probe microscopy (SPM) and Raman spectroscopy, the needle point (such as Au or Ag) controlling to produce surface plasmon resonance (SPR) by SPM approaches the distance (as 1nm) very near with sample, under the irradiation of proper laser, the gap of needle point and sample can inspire SPR, optical electric field in this region of very big enhancing, thus strengthen Raman signal.The spatial resolution of TERS reaches as high as 1nm, breaches optical diffraction limit far away.In addition also there is following advantage in TERS: the first, can obtain pattern and the spectral information of sample simultaneously; The second, monomolecular detection sensitivity can be reached, the 3rd, particular/special requirement is not had to sample.These advantages make TERS be applied widely in fields such as biology, material, molectronicses.But TERS is difficult to work in solution environmental, particularly also TERS is not applied to the report of electrochemical research at present, key issue is wherein to lack the electrolytic cell being applicable to TERS.
Summary of the invention
The present invention devises the electrolytic cell that one is applicable to Tip-Enhanced Raman Spectroscopy technology (TERS), TERS can be applied to electrochemical research by it, solves the problem that transmission spectra electrochemical techniques spatial resolution is limited to optical diffraction limit.Structure of the present invention is simple, easy to assembly.
Technical scheme of the present invention is as follows:
A kind of electrolytic cell being applicable to Tip-Enhanced Raman Spectroscopy technology, it is characterized in that: this electrolytic cell is installed on the sample stage of TERS instrument, comprise an electrolytic tank body (1), optics window (2), contrast electrode (3), to electrode (4), at least one working electrode (5) and the needle point (6) with TERS activity, wherein:
Contrast electrode (3), be directly screwed in electrolytic tank body (1) to electrode (4) and at least one working electrode (5), pond body (1) top is uncovered, and open space is more than or equal to inserting needle and the scanning imagery requisite space of TERS needle point (6); Pond body (1) side direction has otch, and incision pastes optics window (2); Laser incidence and Raman signal collection are all passed through same object lens (7) and are realized, and the optical axis of object lens (7) is vertical with optics window (2); Be provided with the inclined-plane towards optics window bottom the body of pond, working electrode (5) is installed on this inclined-plane; This needle point (6) inserts in pond body (1), and end is in working electrode (5) top.
In the preferred embodiment, working electrode (5) is testing sample, can comprise at least one in metal single crystal, graphite or level and smooth conduction plated film substrate etc.Contrast electrode can adopt precious metal, silver/silver chloride electrode etc.; The inert electrodes such as precious metal can be adopted to electrode;
In the preferred embodiment, if TERS instrument can the current potential of control TERS needle point, this electrolytic cell can also comprise one second working electrode needle point, forms four electrode systems.
In the preferred embodiment, described optics window (2) is made for light transmissive material.
In the preferred embodiment, pond body bottom faces, to the inclined-plane of optics window (2), is 0-80 ° with the angle of horizontal direction.Be more preferred from 10-30 degree.
In the preferred embodiment, needle point (6) is installed on the scanner head of TERS instrument.
In the preferred embodiment, described TERS instrument comprises based on the one in scanning tunnel microscope (STM), atomic force microscope (AFM), scanning shear force microscope (SFM).
A kind of Tip-Enhanced Raman Spectroscopy detection method, comprises the steps:
(1) electrolytic cell as the aforementioned is set up,
(2) add suitable solution in electrolytic cell, Electrode connection, to electrochemical workstation, carries out electrochemical control;
(3) TERS needle point inserting needle, regulates object lens position, makes laser excitation and Raman signal collection reach optimum condition;
(4) spectra collection.
Advantage of the present invention is as follows:
1, electrolytic cell of the present invention, makes TERS can work in electrochemical solution environment;
2, laser incidence and Raman signal collection are all realized by same object lens, and optical axis is vertical with optics window.Be the inclined-plane (be 0-80 ° with horizontal direction angle) towards optics window bottom the body of pond, for installment work electrode, this designs the stop reduced light, improves launching efficiency and Raman signal intensity.
3, of the present invention highly sensitive, can individual layer on testing electrode or subband structures binding molecule.
4, the electrolytic cell being applicable to TERS that the present invention relates to, except possessing perfect electrochemical function, also take into account the many-sided requirement of TERS, therefore TERS can be applied to electrochemical research by it, greatly improve the spatial resolution of traditional spectroelectrochemistry technology, effects on surface science is significant.
Accompanying drawing explanation
Fig. 1 is that schematic diagram is cutd open in side of the present invention;
Fig. 2 is perspective view of the present invention;
Fig. 3 is electrolytic tank body perspective view of the present invention;
Fig. 4 be in embodiments of the invention STM to the golden monocrystalline imaging of inclination 20 °;
Fig. 5 is the TERS spectral signal in embodiments of the invention under needle point inserting needle and withdraw of the needle state;
Fig. 6 is the original position TERS spectral signal in embodiments of the invention under different potentials.
Embodiment
Concrete embodiment, illustrates present embodiment below in conjunction with accompanying drawing.The electrolytic cell that can be used in TERS described in this Example embodiments, comprises an electrolytic tank body, optics window, contrast electrode, to electrode, working electrode, and electrolytic cell is be applicable to the particular design that TERS makes.
(1) assembling of electrolytic cell
See Fig. 1 to Fig. 3, optics window (2) is attached in the lateral incision of electrolytic tank body (1) with melt viscosity, then by contrast electrode (3), be fixed in electrolytic tank body (1) electrode (4), working electrode (5) teflon screw.Whole electrolytic cell screw is installed on TERS instrument.Finally by three Electrode connection to electrochemical workstation, add appropriate solution.
(2) TERS needle point inserting needle
Be installed on the scanner head of TERS instrument by the needle point (6) with TERS activity, coarse adjustment tip position, makes tip end be in above working electrode.Inserting needle parameter is set, inserting needle.
(3) spectra collection
Laser excitation and Raman signal collection are all passed through same object lens (7) and are realized.Regulate the position of object lens (7), white light imaging system auxiliary under, make Laser Focusing to the gap of needle point and sample.Gather TERS signal, the position of fine setting object lens (7), laser excitation and Raman signal are collected and reaches optimum condition, now TERS signal is the strongest.Change electrochemical control condition, measure the TERS signal in electrochemical process.
Embodiment 1
(1) electrode prepares
Contrast electrode is the platinum filament of diameter 0.5mm, is platinum black electrode to electrode.Working electrode is commercial golden monocrystalline, and after electrochemical polish and annealing in process, golden monocrystalline immerses in the ethanolic solution of 4-sulfydryl-4'-(4-pyridine) biphenyl, and take out after one hour, with a large amount of alcohol flushings, nitrogen dries up.
(2) electrolytic cell assembling
With hot melt adhesive, cover glass thick for 0.17mm is pasted on the otch of electrolytic tank body side direction.With teflon screw, three electrodes are fixed in electrolytic tank body.Whole electrolytic cell is installed on the sample stage of scanning tunnel microscope (STM) by direct screw, and three electrodes are received electrochemical workstation.The 0.1M sodium perchlorate aqueous solution of about 0.2mL is added in electrolytic cell.The electrolytic cell adopted in this example, side, pond to otch be vertical direction, being inclined-plane bottom the body of pond, is 20 ° with the angle of horizontal direction.
(3) STM inserting needle
Adopt the acupuncture needle point of electrochemical etching in this example, and encapsulate with nail polish.Needle point is installed on scanner head, coarse adjustment tip position, tip end is positioned at above working electrode.STM inserting needle parameter is set, inserting needle.From the STM imaging results of Fig. 4, golden monocrystalline quality is better, and step is very clear.
(4) TERS spectra collection
Regulate the position of object lens by XYZ three-dimensional machinery displacement platform, white light imaging system auxiliary under, make 633nm Laser Focusing to the gap of needle point and sample.Then close white light, gather TERS signal, fine setting XYZ three-D displacement platform, laser excitation and Raman signal are collected and reaches optimum condition, now TERS signal is the strongest.Fig. 5 is under open circuit potential, the TERS spectrum under needle point inserting needle and withdraw of the needle condition.When needle point inserting needle, the TERS signal of 4-sulfydryl-4'-(4-pyridine) biphenyl molecule is stronger; After the needle point withdraw of the needle, owing to there is no enhancement effect, do not detect the signal of any testing molecule.Fig. 6 is the TERS spectrum being controlled by working electrode to measure under different potentials, current potential steps to 0.1V by-0.7V, the relative intensity obviously can observing spectrum peak, 1189cm-1 place changes from weak to strong, this shows, after current potential changes, molecule there occurs marked change at the adsorbed state of single-crystal surface or molecular structure.
Above embodiment only for technical conceive of the present invention and feature are described, can not limit the scope of the invention with this.All equivalence changes done according to Spirit Essence of the present invention, all should be encompassed within protection scope of the present invention.
Claims (8)
1. one kind is applicable to the electrolytic cell of Tip-Enhanced Raman Spectroscopy technology, this electrolytic cell is installed on the sample stage of TERS instrument, comprise an electrolytic tank body (1), optics window (2), contrast electrode (3), to electrode (4) and at least one working electrode (5) wherein, contrast electrode (3), electrode (4) and at least one working electrode (5) to be directly screwed in electrolytic tank body (1), to it is characterized in that:
Also comprise the needle point (6) with TERS activity; Pond body (1) top is uncovered, and open space is more than or equal to inserting needle and the scanning imagery requisite space of TERS needle point (6); Pond body (1) side direction has otch, and incision pastes optics window (2); Laser incidence and Raman signal collection are all passed through same object lens (7) and are realized, and the optical axis of object lens (7) is vertical with optics window (2); Be provided with the inclined-plane towards optics window bottom the body of pond, working electrode (5) is installed on this inclined-plane; This needle point (6) inserts in pond body (1), and end is in working electrode (5) top.
2. a kind of electrolytic cell being applicable to Tip-Enhanced Raman Spectroscopy technology as claimed in claim 1, is characterized in that: working electrode (5) is testing sample, comprises at least one in metal single crystal, graphite or level and smooth conduction plated film substrate.
3. a kind of electrolytic cell being applicable to Tip-Enhanced Raman Spectroscopy technology as claimed in claim 1, is characterized in that: also comprise one second working electrode needle point, form four electrode systems.
4. a kind of electrolytic cell being applicable to Tip-Enhanced Raman Spectroscopy technology as claimed in claim 1, is characterized in that: described optics window (2) is made for light transmissive material.
5. a kind of electrolytic cell being applicable to Tip-Enhanced Raman Spectroscopy technology as claimed in claim 1, is characterized in that: pond body bottom faces, to the inclined-plane of optics window (2), is 0-80 ° with the angle of horizontal direction.
6. a kind of electrolytic cell being applicable to Tip-Enhanced Raman Spectroscopy technology as claimed in claim 1, is characterized in that: needle point (6) is installed on the scanner head of TERS instrument.
7. a kind of electrolytic cell being applicable to Tip-Enhanced Raman Spectroscopy technology as claimed in claim 1, is characterized in that: described TERS instrument comprises based on the one in scanning tunnel microscope (STM), atomic force microscope (AFM), scanning shear force microscope (SFM).
8. a Tip-Enhanced Raman Spectroscopy detection method, comprises the steps:
(1) electrolytic cell as described in any one of claim 1 to 7 is set up,
(2) add suitable solution in electrolytic cell, Electrode connection, to electrochemical workstation, carries out electrochemical control;
(3) TERS needle point inserting needle, regulates object lens position, makes laser excitation and Raman signal collection reach optimum condition;
(4) spectra collection.
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| CN104502324B (en) * | 2014-12-29 | 2017-04-05 | 东北大学 | Melten salt electriochemistry original position Raman spectral measurement microscopic heating stands |
| CN107192860A (en) * | 2016-03-14 | 2017-09-22 | 江苏卓芯电子科技有限公司 | Two kinds with magnetic-type and optical observation window cell design |
| DE102016222613B3 (en) | 2016-11-17 | 2018-05-03 | Universität Ulm | Measuring cell for Raman spectroscopy at a solid-liquid interface and uses thereof |
| CN110031450A (en) * | 2019-05-15 | 2019-07-19 | 兰州大学 | Open convenient water system in-situ Raman electrolytic cell |
| CN112014308A (en) * | 2020-09-07 | 2020-12-01 | 中国石油大学(华东) | Raman-enhanced electrochemical corrosion cell and control method thereof |
| CN112748260B (en) * | 2020-12-23 | 2022-03-08 | 中国科学院长春光学精密机械与物理研究所 | STM (scanning tunneling microscope) needle tip enhanced spectrum acquisition device and acquisition method thereof |
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