WO2024016425A1 - Nanospectromicroscope infrarouge électrochimique et méthode d'analyse - Google Patents

Nanospectromicroscope infrarouge électrochimique et méthode d'analyse Download PDF

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WO2024016425A1
WO2024016425A1 PCT/CN2022/114758 CN2022114758W WO2024016425A1 WO 2024016425 A1 WO2024016425 A1 WO 2024016425A1 CN 2022114758 W CN2022114758 W CN 2022114758W WO 2024016425 A1 WO2024016425 A1 WO 2024016425A1
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infrared
sample
scanning probe
electrochemical
nano
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PCT/CN2022/114758
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Chinese (zh)
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王海龙
易骏
田中群
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厦门大学
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • 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
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01Q—SCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
    • G01Q60/00—Particular types of SPM [Scanning Probe Microscopy] or microscopes; Essential components thereof
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01Q—SCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
    • G01Q60/00—Particular types of SPM [Scanning Probe Microscopy] or microscopes; Essential components thereof
    • G01Q60/24—AFM [Atomic Force Microscopy] or apparatus therefor, e.g. AFM probes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01Q—SCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
    • G01Q60/00—Particular types of SPM [Scanning Probe Microscopy] or microscopes; Essential components thereof
    • G01Q60/24—AFM [Atomic Force Microscopy] or apparatus therefor, e.g. AFM probes
    • G01Q60/38—Probes, their manufacture, or their related instrumentation, e.g. holders

Definitions

  • the invention belongs to the field of electrochemical detection, and specifically relates to an electrochemical nano-infrared spectrum microscope and an analysis method.
  • Electrochemical scanning probe microscopy is a surface detection technology that combines the ultra-high spatial resolution of scanning probe microscopy with the high chemical sensitivity of electrochemical technology.
  • the detection device includes a scanning probe microscope and an electrochemical workstation, which can image the surface morphology of the material surface in an electrochemical in-situ environment.
  • Scanning probe microscopes include atomic force microscopy (AFM), which realizes surface topography observation through the interaction between the probe and the substrate, and scanning tunneling microscopy (STM), which realizes surface topography through tunneling current feedback between the probe and the sample surface.
  • AFM atomic force microscopy
  • STM scanning tunneling microscopy
  • the atomic-level imaging capabilities demonstrated by EC-SPM have played an important role in the development of electrochemical science.
  • Nano-infrared spectroscopy is a detection technology that measures the response of a sample to infrared light through a scanning probe microscope.
  • the detection device includes a mid-infrared laser and a scanning probe microscope, which can achieve infrared spectroscopy and imaging of samples with better than 10nm spatial resolution.
  • Nano-infrared spectroscopy technology is mainly divided into photothermal-induced expansion type, photo-induced force type and scattering type. In recent years, it has played an important role in polymer surface analysis, energy materials, biological analysis and other fields. Despite this, nano-infrared spectroscopy technology still has a lot of room for development in terms of detection sensitivity, spatial resolution, especially the monitoring of controllable chemical reaction processes.
  • Related technologies can be found in the literature: Dmitry Kurouski, et al., Chem.Soc.Rev., 2020, 49, 3315-3347.
  • the present invention provides a new type of electrochemical nano-infrared spectroscopic microscope, which can perform nano-infrared analysis on the sample to be measured on the electrode surface under a controllable potential, for example, based on Micro-infrared analysis of photothermal expansion, micro-infrared analysis based on near-field infrared scattering, or micro-infrared analysis based on light induction force, etc.
  • a first aspect of the present disclosure provides an electrochemical nano-infrared spectroscopic microscope (nanoIR-ECSPM), including:
  • Electrochemical detection cell the electrochemical detection cell includes a detection chamber and a wall surrounding the detection chamber, the wall includes an infrared permeable window, and a sample is provided on the inner surface of the infrared permeable window area, the sample area is used to place the sample to be tested;
  • a scanning probe microscope system configured to interact with a sample to be measured located in the sample area through a scanning probe and measure the response of the scanning probe;
  • An infrared radiation source configured to emit infrared radiation toward the sample area from outside the infrared permeable window.
  • the following operations can be performed on the sample to be tested in the electrochemical detection cell: electrochemical analysis, infrared spectrum analysis, and nano-infrared scanning imaging.
  • the above operations can be performed separately or simultaneously.
  • the activity potential of the sample can be obtained by performing electrochemical analysis;
  • the infrared characteristic wavelength of the sample can be obtained by performing infrared spectroscopy analysis;
  • the chemical composition distribution information on the sample surface can be obtained by performing nano-infrared scanning imaging at a set infrared wavelength.
  • the effect of performing nano-infrared spectroscopy detection at this time is to obtain a reaction Spatial distribution of active sites at the nanoscale.
  • the effect of performing nano-infrared spectroscopy detection at this time is to obtain The change in the chemical structure of a substance during a chemical reaction at the active site at the active potential.
  • the infrared light directly interacts with the sample after passing through the infrared permeable window, eliminating the influence of the electrolyte in the electrochemical detection cell on the infrared spectrum analysis. Influence.
  • the infrared transmissive window includes a light concentrator (eg, a total internal reflection prism). Based on this solution, the concentrator can further focus the infrared radiation on the surface of the sample to be measured, thereby improving detection sensitivity.
  • a light concentrator eg, a total internal reflection prism
  • the term “medial side” refers to the side facing the detection chamber.
  • an infrared transparent current collector is disposed under the sample area of the infrared transparent window. Based on this solution, infrared can be placed on the surface of the current collector to place the sample to be tested. Based on this solution, the infrared transparent current collector can establish a good electrical connection with the sample to be tested without blocking the infrared radiation directed to the sample to be tested.
  • the infrared permeable current collector is a metal film, such as a gold film (Au film).
  • the thickness of the gold film is, for example, 5 nm-20 nm, such as 10 nm-15 nm.
  • the infrared transparent current collector has a surface plasmon array structure.
  • Surface plasmon structures can be used to achieve surface-enhanced spectroscopy.
  • the surface plasmon array structure is, for example, any surface plasmon array structure introduced in the following documents: Yang, K., Yao, X., Liu, B., Ren, B., Metallic Plasmonic Array Structures: Principles ,Fabrications,Properties,and Applications.Adv.Mater.2021,33,2007988.
  • an infrared transmissive window is located at the bottom of the electrochemical detection cell.
  • the bottom of the electrochemical detection cell refers to the side of the electrochemical detection cell facing the ground when in use.
  • the scanning probe microscope system is a scanning tunneling microscope system or an atomic force microscope system.
  • the scanning probe microscopy system is an atomic force microscopy system that extracts absorption signals from contact resonances with the scanning probe as the sample expands or contracts, the expansion or contraction It is caused by infrared radiation in the sample area.
  • the electrochemical nano-infrared spectroscopic microscope includes an atomic force microscope-based infrared analysis system (AFM-IR) that performs analysis through the scanning probe microscope system and the infrared radiation source.
  • AFM-IR atomic force microscope-based infrared analysis system
  • the electrochemical nano-infrared spectroscopic microscope further includes a scattered light detector that collects scattered light emitted from the sample area caused by infrared radiation in the sample area.
  • electrochemical nanoinfrared spectroscopic microscopy includes scattering scanning near-field optical microscopy (s-SNOM) performed by the scanning probe microscopy system and the infrared radiation source. analyze.
  • s-SNOM scattering scanning near-field optical microscopy
  • the electrochemical nano-infrared spectroscopic microscope also includes one or more of the following:
  • a first driving device drives the electrochemical detection cell to move
  • the second driving device drives the focusing mirror to move, and the focusing mirror is used to move the infrared radiation source.
  • the infrared transmissive window is located at the bottom of the electrochemical detection cell.
  • the electrochemical detection cell includes a wall that includes a window frame, and the infrared-transmissive window is removably and sealingly connected to the window frame.
  • the infrared transparent window is made of an infrared transparent material.
  • the electrochemical nano-infrared spectroscopic microscope also includes an electrochemical workstation, and the electrochemical workstation includes:
  • a first working electrode terminal, the first working electrode terminal is electrically connected to the sample to be measured located in the sample area (for example, the sample to be measured is electrically connected to the sample to be measured through an infrared permeable current collector);
  • the counter electrode terminal is electrically connected to the counter electrode located in the electrochemical detection cell.
  • the electrochemical workstation further includes:
  • the second working electrode terminal is electrically connected to the scanning probe.
  • a scanning probe inlet is also provided on the wall of the electrochemical detection cell, and the scanning probe inlet allows the scanning probe to extend into the chamber.
  • a scanning probe microscope system includes a scanning probe and a scanning probe deflection detection assembly
  • the scanning probe deflection detection component includes:
  • Positioning laser used to emit positioning laser to the scanning probe
  • Position-sensitive detector is used to receive the reflected light of the positioning laser on the scanning probe.
  • the infrared radiation source is an infrared laser
  • the infrared radiation source is an infrared pulse laser
  • the infrared radiation source is a mid-infrared laser
  • the infrared radiation source is a quantum cascade laser.
  • the scanning probe is made of silicon, silicon oxide or silicon nitride.
  • the surface of the scanning probe may be covered with a conductive layer
  • the conductive layer is made of metal
  • the conductive layer is made of one or more of the following: gold, platinum.
  • the present disclosure provides a sample analysis method, including
  • the above sample analysis method further includes performing any of the following operations:
  • -Collect infrared spectrum control the active potential between the scanning probe and the counter electrode, keep the infrared radiation irradiating in the area where the scanning probe interacts with the sample to be measured, control the infrared radiation to scan the wavelength, and collect the response signal of the scanning probe, Based on the change of the response signal with the wavelength of infrared radiation, a nano-infrared spectrum is output;
  • the response signal of the scanning probe is collected in the area where the needle interacts with the sample to be measured, and imaging data is output based on the change of the response signal with the position.
  • the present disclosure provides a sample analysis method, including
  • the scanning probe and the sample to be measured to be at a preset potential, control the infrared radiation to remain at the infrared characteristic wavelength, control the scanning probe to perform position scanning on the surface of the sample to be measured, and keep the infrared radiation irradiating between the scanning probe and the sample to be measured In the area where the sample interacts, the response signal of the scanning probe is collected, and imaging data is output based on the change of the response signal with the position.
  • the sample analysis method of any of the above. In some embodiments, the above sample analysis method also includes performing any of the following operations:
  • the scanning probe and the sample to be measured to be at a preset potential, control the infrared radiation to remain at the infrared characteristic wavelength, control the scanning probe to perform position scanning on the surface of the sample to be measured, and keep the infrared radiation irradiating between the scanning probe and the sample to be measured In the area where the sample interacts, the response signal of the scanning probe is collected, and imaging data is output based on the change of the response signal with the position.
  • SPM scanning probe microscopy
  • a scanning probe microscope may be an atomic force microscope (AFM) that includes a cantilever probe with a sharp tip.
  • AFM atomic force microscope
  • SPM generally includes the ability to measure the motion, position, and/or other response of a probe tip and/or an object to which the probe tip is attached (which can be, for example, a cantilever or a tuning fork or a MEMS device).
  • a cantilever probe bounces a laser beam to measure the deflection of the cantilever.
  • SPM can also use aperture-based probes for delivering light to and/or collecting light from the sample.
  • "scanning probe interacting with a sample to be measured” means bringing the probe tip close enough to the surface of the sample to create one or more near-field interactions, such as tip-sample force attraction and/or repulsion, and/or the generation and/or amplification of radiation scattered from the sample area near the probe apex.
  • the interaction can be contact mode, intermittent contact/tapping mode, non-contact mode, shear mode, pulsed force mode, and/or any lateral modulation mode.
  • the interaction can be constant, or in some cases can be periodic.
  • Periodic interactions can be sinusoidal or any arbitrary periodic waveform. Pulsed force mode and/or fast force profiling techniques may also be used to periodically bring the probe to a desired level of interaction with the sample and, after a holding period, retract the probe.
  • Illuminating refers to directing radiation to a subject (eg, a surface of a sample, a probe tip, and/or a region of probe-sample interaction). Illumination can include radiation in the infrared wavelength range, the visible light range, and other wavelength ranges from ultraviolet to terahertz. Illumination may include any configuration of radiation sources, reflective elements, focusing elements, and any other beam control or conditioning elements.
  • an "infrared radiation source” refers to one or more light sources that generate or emit radiation in the infrared wavelength range, generally mid-infrared between 2-50 microns. Infrared light sources can produce radiation in the entire range described above, or in many cases, can be tuned in a subset of the range described above (e.g., 2.5-4 microns or 5-13 microns).
  • the radiation source can be one of a variety of sources, including a heat source or a carbon silicon rod (Globar) light source, a supercontinuum laser source, a frequency comb, a difference frequency generator, and a sum frequency ) generators, harmonic generators, optical parametric oscillators (OPO), optical parametric generators (OPG), quantum cascade lasers (QCL), nanosecond, picosecond and femtosecond laser systems, CO2 lasers, heated cantilevers Probe or other microscopic heater, and/or any other source that produces a radiation beam.
  • the source emits infrared radiation, and in other cases, may instead or can also emit radiation in other wavelength ranges, such as from ultraviolet to terahertz (THz).
  • the source may be narrowband, such as with a spectral width less than 10 cm “1 or less than 1 cm “1 , or may be broadband, such as with a spectral width greater than 10 cm “1 , 100 cm “1 or 500 cm “1 .
  • spectrum refers to measuring one or more properties of a sample as a function of wavelength, or equivalently (and more commonly) as a function of wavenumber.
  • infrared absorption spectrum refers to a spectrum that is proportional to a wavelength dependent on the infrared absorption coefficient, absorbance, or similar indication of infrared absorption properties of the sample.
  • An example of infrared absorption spectroscopy is the absorption measurement produced by a Fourier transform infrared spectrometer (FTIR), also known as FTIR absorption spectroscopy. (Note that IR absorption spectra can also be easily derived from transmission spectra.)
  • the scanning probe microscope system includes a scanning probe microscope controller, which refers to a system that facilitates data acquisition and control of the AFM-IR system.
  • the controller may be a single integrated electronics enclosure or may include multiple distributed components.
  • the control element may control the positioning and/or scanning of the probe tip and/or sample. Data on probe deflection, motion, or other responses may also be collected to provide control of radiation source power, polarization, steering, focus, and/or other functions.
  • Control elements and the like may include computer program means or digital logic means, and may use a variety of computing devices (computers, personal electronic devices), analog and/or digital discrete circuit components (transistors, resistors, capacitors, inductors, diodes, etc.) , programmable logic, microprocessors, microcontrollers, application-specific integrated circuits, or any combination of other circuit components.
  • Memory is used to store computer programs, executable with discrete circuit components to implement one or more processes described herein.
  • detector in the context of probing a beam refers to an optical detector that generates a signal indicative of the amount of light incident on the detector.
  • the detector may be any of a variety of optical detectors, including but not limited to silicon PIN photodiodes, gallium phosphide photodetectors, other semiconductor detectors, avalanche photodiodes, photomultiplier tubes, and/or generate indicators incident on Other detector technologies that signal the amount of light on the detector surface.
  • the detector may also be a fluorometer and/or a Raman spectrometer.
  • electrochemical tunneling microscopy is any one described in the following documents. Wan Lijun. Nanoscience and Technology: Electrochemical Scanning Tunneling Microscopy and Its Application[M]. Science Press, 2015. Yan Jiawei, Zhan Dongping, Mao Bingwei. Scanning probe microscopy and its application in electrochemistry [J]. Journal of Xiamen University (Natural Science Edition), 2020(5).
  • the "electrochemical atomic force microscope” is any one described in the following documents: Sun Shigang et al., Principles and Methods of Electrochemical Measurement, Xiamen University Press, 2021. Cai Shen, Guohong Hu, Ling-Zhi Cheong, Shiqiang Huang, Ji-Guang Zhang, Deyu Wang, Direct Observation of the Growth of Lithium Dendrites on Graphite Anodes by Operando EC-AFM, Small Methods, 2018, 2, 1700298.
  • nano-infrared spectroscopy techniques include s-SNOM techniques performed in IR, which is a useful technique for measuring and mapping the optical properties/material composition of some surfaces with micro-nano resolution.
  • s-SNOM techniques performed in IR
  • Various aspects of this technology are described in U.S. Application Nos. 13/835,312, 14/322,768, 14/634,859, 14/957,480, and 15/249,433 to the present application's co-inventors. These applications are incorporated herein by reference in their entirety.
  • nano-infrared spectroscopy technology includes atomic force microscopy-based infrared analysis system (AFM-IR) technology, which is useful for measuring and mapping the optical properties/material composition of some surfaces with micro-nano resolution. technology.
  • AFM-IR atomic force microscopy-based infrared analysis system
  • Various aspects of this technology are disclosed in U.S. Patents 8869602, 8680457, 8402819, 8001830, 9134341, 8646319, 8242448 and U.S. Patent Applications 13/135,956 and 15/348,848, co-inventors of the present application; and Dazzi A, Prater C B. AFM- IR: Technology and Applications in Nanoscale Infrared Spectroscopy and Chemical Imaging[J]. Chemical Reviews, 2016.
  • the term "infrared transparent” refers to a transmittance to infrared radiation of more than 50%, such as more than 60%, such as more than 70%, such as more than 80%, such as more than 90%, such as 90 to 100%.
  • the present invention provides a new type of electrochemical nano-infrared spectroscopic microscope that can perform nano-infrared analysis of the sample to be measured under a controllable potential (such as nano-infrared analysis based on photothermal expansion or based on near-field infrared Scattering nano-IR analysis, or nano-IR analysis based on light induction);
  • the present invention provides a new electrochemical nano-infrared spectroscopic analysis method, which can perform nano-infrared analysis on the sample to be measured under a controllable potential (for example, micro-infrared analysis based on photothermal expansion or based on near-field infrared scattering) Microscopic infrared analysis);
  • the present invention provides a new electrochemical nano-infrared spectrum microscope, which includes a new electrochemical detection cell.
  • the new electrochemical detection cell has an infrared permeable window, and a sample area is provided on the inner surface of the infrared permeable window. Based on this, infrared radiation directly radiates the sample to be measured through the infrared transmitter window without passing through the electrolyte. In this way, the influence of the electrolyte on infrared radiation is avoided, and the detection accuracy and sensitivity are improved.
  • the structure of the infrared transparent window can include a total internal reflection prism.
  • the infrared radiation is focused on the prism surface through the total internal reflection prism and undergoes total internal reflection, thereby improving the detection sensitivity.
  • the sample area of the infrared transparent window is equipped with an infrared transparent current collector.
  • the current collector is electrically connected to the sample to be tested, which helps to better collect the current of the sample to be tested.
  • the infrared permeable current collector has a surface plasmon array structure, which is designed to further enhance the infrared radiation electric field in a local range, thereby improving detection sensitivity.
  • Figure 1 shows a schematic diagram of some embodiments of an electrochemical nano-infrared spectroscopic microscope.
  • Figure 2 shows a schematic diagram of an electrochemical nano-infrared spectroscopic microscope of still some embodiments.
  • Figure 3 shows a schematic diagram of the electrochemical detection cell of the electrochemical nano-infrared spectroscopic microscope of some further embodiments.
  • Figure 4 shows a schematic diagram of the electrochemical detection cell of the electrochemical nano-infrared spectroscopic microscope in some further embodiments.
  • Figure 5 shows a partial schematic diagram of the electrochemical detection cell of the electrochemical nano-infrared spectroscopic microscope of some further embodiments.
  • Figure 6 shows the CV curve obtained by cyclic voltammetric scanning detection of the sample to be tested and the counter electrode;
  • Figure 6 (b) shows the potential-free nano-infrared spectrum of the sample to be tested, at -0.25V potential Infrared spectrum under 0.25V potential.
  • the sample shows overall intensity changes in its absorption of infrared light.
  • (c) of Figure 6 shows the infrared imaging image of the sample to be tested at a potential of -0.25V.
  • (d) of Figure 6 shows the infrared imaging image of the sample to be tested at a potential of -0.25V.
  • Figure 7(a) shows a schematic diagram of an electrochemical nano-infrared spectroscopic microscope of some embodiments.
  • (b) of Figure 7 shows the AFM scanning imaging of the surface structural features of the 10 nm gold film by the scanning probe.
  • (c) of Figure 7 shows the AFM scanning imaging of the surface structural characteristics of the PNTP-modified gold film by the scanning probe.
  • (d) of Figure 7 shows the CV curves of cyclic voltammetry scans performed on the original gold film and the PNTP-modified gold film.
  • Figure 7(e) shows the infrared spectrum after each cycle of cyclic voltammetry scanning.
  • (f) of Figure 7 shows the nanometer infrared spectrum scanning imaging obtained at the corresponding characteristic wave number of nitrothiophenol (1505 cm -1 ).
  • (g) of Figure 7 shows the nano-infrared spectrum scanning imaging obtained at the characteristic wave number corresponding to the characteristic wave number of PATP (1594 cm - 1 ).
  • Figure 8(a) shows a schematic diagram of an electrochemical nano-infrared spectroscopic microscope of some embodiments.
  • (b) and (c) of FIG. 8 respectively show photos of the initial gold film and photos of the gold film on which PANI has been deposited.
  • (d) of FIG. 8 shows the CV curve of each cycle of cyclic voltammetry scan.
  • (e) of Figure 8 shows the infrared spectrum curves obtained by performing infrared spectrum scans on the gold film and BAF 2 before performing the cyclic voltammetry scan.
  • (f) of Figure 8 shows the AFM scanning image of the gold film deposited with PANI after 8 cyclic voltammetry scans.
  • Figure 8(g) shows that nano-infrared spectrum scanning imaging was performed on the sample after scanning in the 8th week.
  • Figure 1 shows a schematic diagram of an electrochemical nano-infrared spectroscopic microscope (EC-nanoIR) of some embodiments.
  • Figure 2 shows a schematic diagram of electrochemical nano-infrared spectroscopic microscopy (EC-nanoIR) of further embodiments.
  • Figure 3 shows a partial schematic diagram of the electrochemical detection cell of the electrochemical nano-infrared spectroscopic microscope (EC-nanoIR) of some further embodiments. As shown in Figures 1 to 3:
  • Figure 1 illustrates an electrochemical nano-infrared spectroscopic microscope (EC-nanoIR), including:
  • Electrochemical detection cell 10 includes: a detection chamber 11 and a wall 12 surrounding the detection chamber.
  • the wall 12 includes an infrared transparent window 121.
  • the infrared transparent window A sample area 123 is provided on the inner surface of 121, and the sample area 123 is used to place the sample 13 to be tested;
  • the scanning probe microscope system 20 is configured to interact with the sample to be measured 13 located in the sample area 123 through the scanning probe 21, and measure the response of the scanning probe 21;
  • Infrared radiation source 30 is configured to emit infrared radiation 32 from the outside of the infrared transmittable window 121 to the sample area 123 .
  • the above-mentioned new electrochemical nano-infrared spectroscopic microscope includes a new electrochemical detection cell 10.
  • the new electrochemical detection cell 10 has an infrared permeable window 121, and a sample area 123 is provided on the inner surface of the infrared permeable window 121. . Based on this, the infrared radiation 32 directly radiates the sample 13 to be measured after passing through the infrared transparent window 121 without passing through the electrolyte. In this way, the influence of the electrolyte on infrared radiation is avoided, and the detection accuracy and sensitivity are improved.
  • the scanning probe microscope system is a scanning tunneling microscope system or an atomic force microscope system.
  • the scanning probe microscope system is an atomic force microscopy system, and the scanning probe microscope system extracts absorption signals from contact resonances with the scanning probe when the sample expands or contracts, the expansion or contraction It is caused by infrared radiation in the sample area;
  • the electrochemical nano-infrared spectroscopic microscope includes an atomic force microscope-based infrared analysis system (AFM-IR), which performs analysis through the scanning probe microscope system 20 and the infrared radiation source 30 .
  • AFM-IR atomic force microscope-based infrared analysis system
  • the electrochemical nano-infrared spectroscopic microscope further includes a scattered light detector that collects scattered light emitted from the sample area, where the scattered light is caused by infrared radiation in the sample area;
  • the electrochemical nano-infrared spectroscopic microscope includes a scattering scanning near-field optical microscope (s-SNOM), which is combined with the infrared radiation source through the scanning probe microscope system 20 30Perform analysis.
  • s-SNOM scattering scanning near-field optical microscope
  • the electrochemical nano-infrared spectroscopic microscope further includes a first driving device 51, and the first driving device 51 drives the electrochemical detection cell to move.
  • the electrochemical nano-infrared spectroscopic microscope further includes a second driving device 52 that drives the focusing mirror 34 to move, and the focusing mirror 34 is used to move the infrared radiation source.
  • the infrared transparent window 121 is located at the bottom of the electrochemical detection cell 10 .
  • the wall 12 of the electrochemical detection cell 10 includes a window frame 122, and the infrared transmissive window 121 is detachably and sealingly connected to the window frame 122.
  • the infrared transparent window 121 is made of an infrared transparent material.
  • the electrochemical nano-infrared spectroscopic microscope also includes an electrochemical workstation, and the electrochemical workstation includes:
  • the first working electrode terminal 41 is electrically connected to the sample to be tested 13 located in the sample area;
  • Reference electrode terminal 43 which is electrically connected to the reference electrode 143 located in the electrochemical detection cell.
  • the counter electrode terminal 44 is electrically connected to the counter electrode 144 located in the electrochemical detection cell.
  • the electrochemical workstation further includes:
  • the second working electrode terminal 42 is electrically connected to the scanning probe 21 .
  • a scanning probe inlet is provided on the wall 12 of the electrochemical detection cell 10 , and the scanning probe inlet allows the scanning probe 21 to extend into the chamber 12 .
  • the scanning probe microscope system 20 includes a scanning probe 21 and a scanning probe deflection detection assembly 22 .
  • the scanning probe deflection detection component 22 includes:
  • the position sensitive detector 222 is used to receive the reflected light of the positioning laser on the scanning probe.
  • the position-sensitive detector 222 is an optoelectronic device that is sensitive to the position of the incident light point on its photosensitive surface. That is, when the incident light point falls on different positions on the photosensitive surface of the device, different electrical signals will be output accordingly.
  • the scanning probe microscope system 20 further includes a position signal processing module 23 .
  • the position signal processing system module 23 receives the electrical signal output from the position sensitive detector 222 and processes it to determine the position of the incident light point on the photosensitive surface of the position sensitive detector 222 .
  • the infrared radiation source 30 is an infrared laser.
  • the infrared radiation source 30 is an infrared pulse laser.
  • the infrared radiation source 30 is a mid-infrared laser.
  • the infrared radiation source 30 is a quantum cascade laser.
  • the scanning probe is made of silicon, silicon oxide or silicon nitride.
  • the surface of the scanning probe is covered with a conductive layer.
  • the conductive layer is made of metal.
  • the conductive layer is made of one or more of the following: gold, platinum.
  • infrared transmissive window 121 includes a light collector 124 (eg, a total internal reflection prism). Based on this solution, infrared radiation 31 acts on the sample 13 to be measured through the concentrator 124, and the concentrator 124 can focus the infrared radiation on the sample 13 to be measured, thereby improving detection sensitivity.
  • a light collector 124 eg, a total internal reflection prism
  • an infrared transparent current collector 125 is disposed on the sample area 123 of the infrared transparent window 121 . Based on this solution, the infrared transparent current collector 125 is used to place the sample 13 to be tested. Based on this solution, the infrared transparent current collector 125 can establish a good electrical connection with the sample 13 to be tested without blocking the infrared radiation 32 directed to the sample 13 to be tested. The infrared transparent current collector 125 can be electrically connected to the first working electrode terminal 41 , thereby establishing an electrical connection between the first working electrode terminal 41 and the sample 13 to be tested.
  • the present application provides a sample analysis method, including
  • the present application provides a sample analysis method, including
  • the radiation 32 irradiates the area where the scanning probe 21 interacts with the sample 13 to be measured, collects the response signal of the scanning probe 21, and outputs imaging data based on the change of the response signal with the position.
  • a sample analysis method comprising
  • a preset infrared wavelength such as infrared characteristic wavelength
  • the infrared characteristic wavelength may be one or more infrared characteristic absorption wavelengths, that is, the wavelength position corresponding to the infrared characteristic absorption peak.
  • a sample analysis method comprising
  • the electrolyte and the sample to be measured 13 are arranged in the sample area 123 of the electrochemical detection cell 10;
  • a preset potential such as active potential
  • NanoIR spectroscopy Electrochemical nano-infrared spectroscopy at active potential (nano-infrared spectroscopy can be referred to as nanoIR spectroscopy).
  • the electrochemical workstation 40 controls the potential of the reference electrode 143, scans the potential of the sample to be tested 13 relative to the counter electrode 144, and simultaneously measures the current of the sample to be tested 13, to obtain the cyclic voltammogram curve of the sample to be tested 13 in the electrolyte, and determine the electrochemical activity potential.
  • the infrared radiation 32 outputs an infrared light pulse, and along with the infrared light pulse, the position of the deflected light reflected from the back of the cantilever of the scanning probe 21 changes.
  • the position signal of the change in deflected light is extracted and Fourier transformed to extract the amplitude intensity.
  • the obtained curve is the active potential Nano-infrared spectrum of the surface of sample 13 to be tested.
  • nanoscale simultaneous chemical and mechanical imaging via peak force infared microscopy L.Wang, H.Wang, et al.Science Advances. (2017). This document is fully cited here.
  • the scanning probe 21 Further select a specific infrared characteristic wavelength in the nano-infrared spectrum as the infrared light to excite the scanning probe 21, extract the position signal of the change in the deflected light, and obtain the amplitude intensity after Fourier transformation.
  • the scanning probe 21 is used to perform scanning on the surface of the sample 13 to be tested, and the amplitude intensity distribution of the set scanning area on the surface of the sample 13 to be tested is obtained, thereby obtaining the chemical distribution of a certain species at the active potential.
  • Analysis mode 2 Scanning electrochemical nano-infrared spectrum.
  • a cyclic voltammogram scan is performed between the sample 13 to be tested and the counter electrode 144 to obtain a cyclic voltammogram curve on the surface of the sample 13 to be tested, and then determine the electrochemical activity potential.
  • the active potential between the sample 13 to be measured and the counter electrode 144 is maintained, and the scanning probe 21 is controlled to have a potential difference relative to the sample 13 to be measured. Scan the position of the scanning probe 21 on the surface of the sample 13 to be tested, record the current of the scanning probe 21, and plot the current and position of the scanning probe 21 to obtain the spatial distribution of active sites (areas) on the surface of the sample electrode 13.
  • the scanning probe 21 is controlled to be located at the active site (area) on the surface of the sample 13 to be measured, and the focused spot of the infrared radiation 32 is kept coincident with the tip of the scanning probe 21 .
  • the infrared radiation source 30 is controlled to emit infrared light pulses.
  • the four-quadrant photodetector 222 collects the response position signal generated by the deflected light reflected from the cantilever back of the scanning probe 21, performs Fourier transform on the response signal, obtains the amplitude intensity of the response of the scanning probe 21 at the wavelength, and converts the amplitude Intensity is defined as the infrared light signal at the current infrared light wavelength. Control the infrared radiation 32 to perform wavelength scanning to obtain the nanometer infrared spectrum of the scanning probe 12 at the current active site (region).
  • a potential scan can also be performed between the sample to be measured 13 and the counter electrode 144, and a nanometer infrared spectrum is collected at each potential to obtain the change information of the intermediate species at the active site during the potential change process.
  • the potential between the sample 13 to be measured and the counter electrode 144 is controlled to be a preset potential.
  • the scanning probe 21 is controlled to perform position scanning on the surface of the sample 13 to be tested, and infrared imaging of the active sites (areas) on the surface of the sample 13 to be tested is obtained at a characteristic wavelength and a preset potential.
  • cyclic voltammetry scanning is first performed on the sample to be tested and the counter electrode.
  • Figure 6(a) shows the CV curve obtained by performing cyclic voltammetric scanning detection on the sample to be tested and the counter electrode. According to the cyclic voltammetry scan results, it can be known that the activity potentials of the samples to be tested are -0.25V and 0.25V respectively.
  • the infrared spectrum of the sample to be tested was detected under the conditions of 0V potential (initial state of the sample), -0.25V potential, and 0.25V potential to obtain the infrared characteristic peaks of the sample to be tested and the characteristic wavenumbers corresponding to the infrared characteristic peaks.
  • (b) of Figure 6 shows the potential-free nano-infrared spectrum of the sample to be tested, the infrared spectrum at the potential of -0.25V, and the infrared spectrum at the potential of 0.25V.
  • the sample shows overall intensity changes in its absorption of infrared light.
  • Nano-infrared spectrum scanning imaging refers to measuring the infrared spectrum point by point at each position of the sample to be tested, collecting the infrared absorption intensity at each position under the characteristic wave number, giving different infrared absorption intensities different colors, and then drawing the position-infrared absorption intensity image. That is the infrared imaging picture. Comparing (c) and (d) in Figure 6, it can be seen that at the active potential, the refractive index response of the sample to be tested changes significantly in the infrared spectrum region due to the injection and extraction of electrons.
  • nitrothiophenol (PNTP) was used as the sample to be tested, and the electrochemical nano-infrared spectroscopic microscope of the present application was used to analyze and detect the sample to be tested.
  • FIG. 7 shows a schematic diagram of an electrochemical nano-infrared spectroscopic microscope.
  • the material of the infrared transparent window 121 is BaF 2 .
  • the infrared transparent current collector 125 is a gold film with a thickness of 10 nm.
  • a nitrothiophenol self-assembled monolayer (PNTP SAM) is deposited on the infrared permeable current collector 125 .
  • the scanning probe 21 is a silicon (Si) probe.
  • FIG. 7 shows the AFM scanning imaging of the surface structural characteristics of the PNTP-modified gold film by the scanning probe. Comparing (b) and (c) in Figure 7, it can be observed that there are obvious morphological differences between the two, which confirms that the surface of the gold film has been successfully modified by PNTP.
  • Nano-infrared spectrum scanning imaging was performed on the samples scanned in the 6th week.
  • Nano-infrared spectrum scanning imaging refers to measuring the infrared spectrum point by point at each position of the sample to be tested, collecting the infrared absorption intensity at each position under the characteristic wave number, giving different infrared absorption intensities different colors, and then drawing the position-infrared absorption intensity image. That is the infrared imaging picture.
  • (f) of Figure 7 shows the nano-infrared spectrum scanning image of the sample obtained at the characteristic wave number of nitrothiophenol (PNTP) (1505 cm -1 ). The redder the color of the image, the stronger the infrared signal. As shown in (f) of Figure 7, red signals appear in some locations in the picture, indicating that PNTP exists at these locations; but at the same time, signals of other colors appear in some locations in the picture, indicating that the PNTP in these locations has been partially or completely converted into PATP.
  • PNTP nitrothiophenol
  • (g) of Figure 7 shows the nano-infrared spectrum scanning imaging of the sample obtained at the characteristic wave number corresponding to the characteristic wave number of PATP (1594 cm -1 ). The redder the color of the image, the stronger the infrared signal. As shown in (g) of Figure 7 , red signals appear in part of the picture, indicating that PATP has been formed at these locations.
  • the electrochemical nano-infrared spectroscopic microscope of this application was used to observe the process of ANI polymerizing into PANI under the action of electric current.
  • FIG 8(a) shows a schematic diagram of an electrochemical nano-infrared spectrum microscope.
  • the infrared permeable window 121 is made of BaF 2
  • the infrared permeable current collector 125 is a 10 nm gold film
  • the electrolyte is (0.1M H 2 SO 4 +30mM ANI).
  • 8 cyclic voltammetry scans were performed between the infrared permeable current collector 125 and the counter electrode 144.
  • ANI was polymerized into PANI under the action of current and deposited on the infrared permeable current collector 125.
  • the surface of the current collector 125 gold film).
  • FIG. 8 respectively show photos of the initial gold film and photos of the gold film on which PANI has been deposited. Compared with picture (b), the color of the solution and gold film in picture (c) is darker, indicating that PANI is formed in the electrolyte and on the surface of the gold film.
  • Figure 8 (d) shows the CV curve of each cycle of cyclic voltammetry scan. As shown in the figure, from the 1st week to the 8th week of scanning, as the number of scans increases, the current density on the sample surface gradually decreases, which shows that ANI undergoes a polymerization reaction and is converted into PANI during the scanning process, and the reaction rate gradually decreases.
  • FIG. 8 shows the infrared spectrum curves obtained by performing infrared spectrum scans on the gold film and BAF 2 before performing the cyclic voltammetry scan.
  • Figure 8(e) also shows the infrared spectrum curve of the gold film deposited with PANI after eight cyclic voltammetry scans. The characteristic infrared peak at 1500 cm -1 confirms that PANI is indeed formed on the surface of the gold film.
  • FIG. 8 shows the AFM scanning image of the gold film deposited with PANI after 8 cyclic voltammetry scans.
  • Figure 8(g) shows that nano-infrared spectrum scanning imaging was performed on the sample after scanning in the 8th week.
  • Nano-infrared spectrum scanning imaging refers to measuring the infrared spectrum point by point at each position of the sample to be tested, collecting the infrared absorption intensity at each position under the characteristic wave number, giving different infrared absorption intensities different colors, and then drawing the position-infrared absorption intensity image. That is the infrared imaging picture.
  • the characteristic wave number of PANI 1500 cm -1, is used as the infrared scanning wave number.
  • Figure 8 (f) shows that there are convex structural features (light-colored areas) in part of the surface of the gold film, confirming that products are deposited on the surface of the gold film.
  • Figure 8(g) shows that there are characteristic peaks (red areas) corresponding to PANI at some locations on the surface of the gold film, confirming that PANI is deposited on the surface of the gold film. Comparing (f) and (g) of Figure 8, it is found that the light-colored area and the red area can basically overlap, and the two work together to confirm that APNI is indeed formed on the surface of the gold film.

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Abstract

L'invention concerne un nanospectromicroscope infrarouge électrochimique et une méthode d'analyse. Le nanospectromicroscope infrarouge électrochimique comprend : une cellule de détection électrochimique (10), la cellule de détection électrochimique (10) comprenant une cavité de détection (11) et une paroi (12) fermée destinée à former la cavité de détection, la paroi (12) comprenant une fenêtre perméable aux infrarouges (121), une zone d'échantillon (123) étant disposée sur la surface latérale interne de la fenêtre perméable aux infrarouges (121), et la zone d'échantillon (123) étant utilisée pour placer un échantillon à détecter (13) ; un système de microscope à sonde de balayage (20), le système de microscope à sonde de balayage (20) étant configuré pour interagir avec ledit échantillon (13) situé dans la zone d'échantillon (123) au moyen d'une sonde de balayage (21), et mesurer une réponse à partir de la sonde de balayage (21) ; et une source de rayonnement infrarouge (30), la source de rayonnement infrarouge (30) étant configurée pour émettre un rayonnement infrarouge depuis le côté externe de la fenêtre perméable aux infrarouges (121) vers la zone d'échantillon (123).
PCT/CN2022/114758 2022-07-19 2022-08-25 Nanospectromicroscope infrarouge électrochimique et méthode d'analyse WO2024016425A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6437328B1 (en) * 1998-08-03 2002-08-20 The Regents Of The University Of California Hyperbaric hydrothermal atomic force microscope
CN103197102A (zh) * 2013-03-08 2013-07-10 西南大学 基于多功能探针的单细胞/单分子成像光/电综合测试仪
CN103235158A (zh) * 2013-01-10 2013-08-07 北京航空航天大学 一种电化学原子力显微镜探针架-电解池装置
CN103852461A (zh) * 2014-03-28 2014-06-11 厦门大学 一种基于扫描探针显微镜的电化学针尖增强拉曼光谱仪器
CN107727886A (zh) * 2017-10-31 2018-02-23 北京航空航天大学 一种倒置式高速电化学原子力显微镜
CN110573887A (zh) * 2017-03-09 2019-12-13 布鲁克纳米公司 用于基于光热效应的红外扫描近场光学显微镜的方法与装置
CN114088980A (zh) * 2021-12-14 2022-02-25 中国石油大学(北京) 石英晶体微天平耦合原子力显微镜装置及检测方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6437328B1 (en) * 1998-08-03 2002-08-20 The Regents Of The University Of California Hyperbaric hydrothermal atomic force microscope
CN103235158A (zh) * 2013-01-10 2013-08-07 北京航空航天大学 一种电化学原子力显微镜探针架-电解池装置
CN103197102A (zh) * 2013-03-08 2013-07-10 西南大学 基于多功能探针的单细胞/单分子成像光/电综合测试仪
CN103852461A (zh) * 2014-03-28 2014-06-11 厦门大学 一种基于扫描探针显微镜的电化学针尖增强拉曼光谱仪器
CN110573887A (zh) * 2017-03-09 2019-12-13 布鲁克纳米公司 用于基于光热效应的红外扫描近场光学显微镜的方法与装置
CN107727886A (zh) * 2017-10-31 2018-02-23 北京航空航天大学 一种倒置式高速电化学原子力显微镜
CN114088980A (zh) * 2021-12-14 2022-02-25 中国石油大学(北京) 石英晶体微天平耦合原子力显微镜装置及检测方法

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