CN117451653A

CN117451653A - Electrochemical nano infrared spectrum microscope and analysis method

Info

Publication number: CN117451653A
Application number: CN202210847337.0A
Authority: CN
Inventors: 王海龙; 易骏; 田中群
Original assignee: Xiamen University
Current assignee: Xiamen University
Priority date: 2022-07-19
Filing date: 2022-07-19
Publication date: 2024-01-26
Also published as: WO2024016425A1

Abstract

The invention relates to an electrochemical nanometer infrared spectrum microscope and an analysis method. The electrochemical nanometer infrared spectrum microscope comprises: the electrochemical detection cell comprises a detection cavity and a wall surrounding the detection cavity, wherein the wall comprises an infrared permeable window, a sample area is arranged on the inner side surface of the infrared permeable window, and the sample area is used for placing a sample to be detected; a scanning probe microscope system configured to interact with a sample to be measured located in the sample region through the scanning probe and to measure a response of the scanning probe; an infrared radiation source configured to emit infrared radiation from outside the infrared-transparent window toward the sample region.

Description

Electrochemical nano infrared spectrum microscope and analysis method

Technical Field

The invention belongs to the field of electrochemical detection, and particularly relates to an electrochemical nanometer infrared spectrum microscope and an analysis method.

Background

Electrochemical scanning probe microscopy (EC-SPM) is a high chemical sensitivity surface detection technique that combines ultra-high spatial resolution of scanning probe microscopy with electrochemical techniques. The detection device comprises a scanning probe microscope and a set of electrochemical working stations, and can image the surface morphology of the material surface in an electrochemical in-situ environment. Scanning probe microscopes include Atomic Force Microscopes (AFMs) that achieve surface topography by probe and substrate interactions and Scanning Tunneling Microscopes (STMs) that achieve surface topography by probe and sample surface tunneling current feedback. The atomic level imaging capability exhibited by EC-SPM plays an important role in the development of electrochemical science. Nevertheless, there is still a great room for development of EC-SPM in terms of resolution, detection sensitivity, and in particular chemical sensitivity. The related art can be found in literature: electrochemical measurement principles and methods, sun Shigang et al, xiamen university Press, 2021.4.

A nano infrared spectrum microscope is a detection technology for measuring the response of a sample to infrared light through a scanning probe microscope. The detection device comprises a mid-infrared laser and a scanning probe microscope, and can realize the infrared spectrum and imaging of samples with spatial resolution better than 10 nm. The nanometer infrared spectrum technology is mainly divided into photo-thermal induced expansion type, photo-induced force type and scattering type, and plays an important role in the fields of polymer surface analysis, energy materials, biological analysis and the like in recent years. Nevertheless, the nano infrared spectrum technology has great development space in the aspects of detection sensitivity, spatial resolution, particularly monitoring of controllable chemical reaction processes and the like. The related art can be found in literature: dm, ry, kurouski et al, chem. Soc. Rev.,2020,49,3315-3347.

Disclosure of Invention

In order to more deeply characterize an electrochemical system, the invention provides a novel electrochemical nano infrared spectrum microscope which can perform nano infrared analysis, such as micro infrared analysis based on photo-thermal expansion, micro infrared analysis based on near-field infrared scattering or micro infrared analysis based on photo-induced force, on a sample to be tested on the surface of an electrode under a controllable potential.

A first aspect of the present disclosure provides an electrochemical nanoIR-ECSPM comprising:

the electrochemical detection cell comprises a detection cavity and a wall surrounding the detection cavity, wherein the wall comprises an infrared permeable window, a sample area is arranged on the inner side surface of the infrared permeable window, and the sample area is used for placing a sample to be detected;

a scanning probe microscope system configured to interact with a sample to be measured located in a sample region through a scanning probe and to measure a response of the scanning probe;

an infrared radiation source configured to emit infrared radiation from an outer side of the infrared-transparent window toward the sample region.

Based on the scheme, the following operations can be performed on the sample to be detected in the electrochemical detection cell: electrochemical analysis, infrared spectroscopic analysis, and nano infrared scanning imaging. The above operations may be performed separately or simultaneously. The activity potential of the sample can be obtained by performing an electrochemical analysis; the infrared characteristic wavelength of the sample can be obtained by performing infrared spectroscopic analysis; the chemical component distribution information of the sample surface can be obtained by performing nano infrared scanning imaging under the set infrared wavelength.

Compared with the traditional potentioless nano infrared spectrum analysis, when a preset potential (such as an active potential) exists between a sample to be detected and a counter electrode in an electrochemical detection cell, the effect of performing nano infrared spectrum detection is to obtain the spatial distribution of reactive sites under the nanoscale.

Compared with the traditional potentioless nano infrared spectrum analysis, when a preset potential (such as an active potential) exists between a sample to be detected and a scanning probe in an electrochemical detection cell, the effect of performing nano infrared spectrum detection is to obtain the change of the chemical structure of a substance in the chemical reaction process of an active site under the active potential.

Based on the scheme, as the sample area is arranged on the inner side surface of the infrared permeable window, infrared light directly interacts with the sample after passing through the infrared permeable window, and the influence of electrolyte in the electrochemical detection cell on infrared spectrum analysis is eliminated.

In some embodiments, the infrared-transparent window includes a condenser (e.g., a total internal reflection prism). Based on the scheme, the condenser can further focus infrared radiation on the surface of the sample to be detected, so that the detection sensitivity is improved.

In some embodiments, the term "medial side" refers to the side that faces the detection chamber.

In some embodiments, an infrared-transparent current collector is disposed under the sample region of the infrared-transparent window. Based on the scheme, the infrared can penetrate through the surface of the current collector to place a sample to be tested. Based on the scheme, the infrared permeable current collector can establish good electric connection with the sample to be tested, and can not shade infrared radiation emitted to the sample to be tested.

In some embodiments, the infrared-transparent current collector is a metal film, such as a gold film (Au film), having a thickness of, for example, 5nm to 20nm, for example, 10nm to 15nm.

In some embodiments, the infrared-transparent current collector has a surface plasmon array structure thereon. Surface plasmon structures can be used to achieve surface enhanced spectroscopy. The surface plasmon array structure is, for example, any one of the surface plasmon array structures described in the following documents: yang, K., yao, X., liu, B, ren, B, metallic Plasmonic Array Structures Principles, fabrics, properties, and applications.adv.Mater.2021,33,2007988.

In some embodiments, the infrared-transparent 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 that faces the ground in the use state.

In some embodiments, there is no electrolyte between the sample to be tested and the infrared-transparent window. This avoids the electrolyte interfering with the infrared spectrum of the sample.

In some embodiments, the scanning probe microscope system is a scanning tunneling microscope system or an atomic force microscope system.

In some embodiments, the scanning probe microscope system is an atomic force microscope system that extracts the absorption signal from the contact resonance with the scanning probe that occurs when the sample expands or contracts, which expansion or contraction is caused by infrared radiation in the sample region.

Preferably, the electrochemical nano-infrared spectroscopic microscope comprises an atomic force microscope based infrared analysis system (AFM-IR) that performs an analysis with the infrared radiation source by means of the scanning probe microscope system.

In some embodiments, the electrochemical nanoinfrared spectral microscope further comprises a scattered light detector that collects scattered light emanating from the sample region, the scattered light being caused by the sample region being subjected to infrared radiation.

In some embodiments, the electrochemical nanoinfrared spectroscopy microscope comprises a scattering scanning near field optical microscope (s-SNOM) that performs an analysis with the infrared radiation source by the scanning probe microscope system.

In some embodiments, the electrochemical nanoinfrared spectroscopy microscope further comprises one or more of the following:

a first driving device for driving the electrochemical detection cell to move;

and the second driving device drives the focusing mirror to move, and the focusing mirror is used for moving the infrared radiation source.

In some embodiments, the infrared-transparent window is located at the bottom of the electrochemical detection cell.

In some embodiments, the electrochemical detection cell includes a wall including a window frame, the infrared-transparent window being removably sealed to the window frame.

In some embodiments, the infrared-transparent window is made of an infrared-transparent material.

In some embodiments, the electrochemical nanoinfrared spectroscopy microscope further comprises an electrochemical workstation comprising:

a first working electrode terminal electrically connected to the sample to be measured located in the sample region (e.g., electrically connected to the sample to be measured through an infrared-transparent current collector);

the reference electrode end is electrically connected with a reference electrode positioned in the electrochemical detection cell; and

and a counter electrode terminal electrically connected to a counter electrode located in the electrochemical detection cell.

In some embodiments, the electrochemical workstation further comprises:

and the second working electrode end is electrically connected with the scanning probe.

In some embodiments, a scanning probe inlet is also provided in the wall of the electrochemical detection cell, the scanning probe inlet allowing a scanning probe to extend into the chamber.

In some embodiments, a scanning probe microscope system includes a scanning probe and a scanning probe deflection detection assembly;

preferably, the scanning probe deflection detection assembly includes:

the positioning laser is used for emitting positioning laser to the scanning probe;

and the position sensitive detector is used for receiving the reflected light of the positioning laser on the scanning probe.

In some embodiments, the infrared radiation source is an infrared laser;

preferably, the infrared radiation source is an infrared pulsed laser;

preferably, the infrared radiation source is a mid-infrared laser;

preferably, the infrared radiation source is a quantum cascade laser.

In some embodiments, the scanning probe is made of silicon, silicon oxide or silicon nitride.

In some embodiments, the surface of the scanning probe may be coated with a conductive layer;

preferably, the material of the conductive layer comprises metal;

Preferably, the material of the conductive layer includes one or more of the following: gold, platinum.

In some aspects, the present disclosure provides a method of sample analysis comprising

Providing an electrochemical nanoinfrared spectroscopy microscope of any of the above;

electrolyte and a sample to be tested are arranged in a sample area of the electrochemical detection cell, and the following operations are carried out:

-controlling the sample to be measured and the counter electrode to be at a preset potential, controlling the infrared radiation to be kept at an infrared characteristic wavelength, controlling the scanning probe to perform position scanning on the surface of the sample to be measured, keeping the infrared radiation to irradiate the interaction area between the scanning probe and the sample to be measured, collecting the response signal of the scanning probe, and outputting imaging data based on the change of the response signal along with the position.

In some embodiments, the above sample analysis method further comprises performing any one of the following operations:

-determining the activity potential: performing cyclic voltammetry scanning between a sample to be detected and a counter electrode to obtain an active potential;

-acquiring an infrared spectrum: controlling the scanning probe and the counter electrode to be in active potential, keeping infrared radiation irradiated on the interaction area of the scanning probe and the sample to be tested, controlling the infrared radiation to perform wavelength scanning, collecting response signals of the scanning probe, and outputting a nanometer infrared spectrum based on the change of the response signals along with the wavelength of the infrared radiation;

-determining an infrared characteristic wavelength: positioning infrared characteristic peaks from the nanometer infrared spectrum, and determining infrared characteristic wavelengths;

-controlling the sample to be measured and the counter electrode to be at a preset potential (e.g. an active potential), controlling the infrared radiation to be kept at an infrared characteristic wavelength, controlling the scanning probe to perform a position scanning on the surface of the sample to be measured, keeping the infrared radiation to irradiate the area where the scanning probe interacts with the sample to be measured, collecting a response signal of the scanning probe, and outputting imaging data based on the change of the response signal with the position.

In some aspects, the present disclosure provides a sample analysis method comprising

electrolyte and a sample to be tested are arranged in a sample area of the electrochemical detection cell, and any one of the following operations is executed:

-controlling the scanning probe and the sample to be measured at a preset potential, controlling the infrared radiation to be kept at an infrared characteristic wavelength, controlling the scanning probe to perform position scanning on the surface of the sample to be measured, keeping the infrared radiation to irradiate an interaction area between the scanning probe and the sample to be measured, collecting a response signal of the scanning probe, and outputting imaging data based on the change of the response signal along with the position.

In some embodiments, the sample analysis method of any one of the above further comprises performing any one of the following operations:

-determining active sites: controlling the sample to be tested and the scanning probe to be in active potential, and then controlling the scanning probe to perform position scanning on the surface of the sample to be tested;

-acquiring an infrared spectrum: maintaining the irradiation of infrared radiation on the interaction area of the scanning probe and the sample to be tested, controlling the infrared radiation to carry out wavelength scanning, collecting response signals of the scanning probe, and outputting a nanometer infrared spectrum based on the change of the response signals along with the wavelength of the infrared radiation;

In some embodiments, a "Scanning Probe Microscope (SPM)" refers to a microscope that measures one or more properties of a sample surface while scanning the surface after a sharp probe interacts with the sample surface. The scanning probe microscope may be an Atomic Force Microscope (AFM) including a cantilever probe with a sharp tip. SPM generally includes the ability to measure motion, position, and/or other response of a probe tip and/or an object to which the probe tip is attached (e.g., can be a cantilever or tuning fork (tuning fork) or a MEMS device). The most common method involves the use of an optical lever system in which a cantilever probe bounces a laser beam to measure the deflection of the cantilever. Alternatives include self-sensing technologies such as piezoresistive cantilevers, tuning forks, capacitive sensors and other technologies. Other detection systems may measure other properties such as force, force gradient, resonant frequency, temperature and/or other interactions with the surface, or responses to surface interactions. SPM may also use aperture-based probes for delivering light to and/or collecting light from the sample.

In some embodiments, "scanning probe interactions with a sample to be measured" refers to bringing the probe tip sufficiently close to the surface of the sample to create one or more near field interactions, such as attraction and/or repulsion of tip-sample forces, and/or generation and/or amplification of radiation scattered from a sample region near the tip of the probe. The interaction may be a contact mode, intermittent contact/tap mode, non-contact mode, shear mode, pulsed force mode, and/or any lateral modulation mode. The interaction may be constant or, in some cases, periodic. The periodic interaction may be a sine wave or any arbitrary periodic waveform. Pulse force patterns and/or rapid force profile techniques may also be used to periodically bring the probe to a desired level of interaction with the sample and to retract the probe after a hold period.

In some embodiments, "illumination" refers to directing radiation to a subject (e.g., the surface of a sample, a probe tip, and/or a region of probe-sample interaction). Illumination may include radiation in the infrared wavelength range, in the visible range, and in other wavelength ranges from ultraviolet to terahertz. The illumination may include any configuration of radiation sources, reflective elements, focusing elements, and any other beam steering or adjusting elements.

In some embodiments, 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. The infrared light source may radiate within the entire range described above, or in many cases, mayTo be a tuning range (e.g., 2.5-4 microns or 5-13 microns) that is a subset of the above range. The radiation source may be one of a variety of sources including a heat source or silicon carbide (Globar) light source, a supercontinuum laser source, a frequency comb (frequency comb), a difference frequency (difference frequency) generator, a sum frequency (frequency) generator, a harmonic generator, an Optical Parametric Oscillator (OPO), an Optical Parametric Generator (OPG), a Quantum Cascade Laser (QCL), nanosecond, picosecond, and femtosecond laser systems, a CO2 laser, a heated cantilever probe or other microscopic heater, and/or any other source that produces a beam of radiation. In some cases, the source emits infrared radiation, in other cases, radiation of other wavelength ranges (e.g., from ultraviolet light to terahertz (THz)) may be substituted or also emitted. The source may be a narrow band, e.g. a spectral width of less than 10cm ^-1 Or less than 1cm ^-1 Or may be broadband, e.g. having a spectral width greater than 10cm ^-1 、100cm ^-1 Or 500cm ^-1 。

In some embodiments, "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.

In some embodiments, "infrared absorption spectrum" refers to a spectrum proportional to a wavelength that depends on a similar indication of the infrared absorption coefficient, absorbance, or infrared absorption characteristics of a sample. An example of infrared absorption spectroscopy is absorption measurement produced by fourier transform infrared spectroscopy (FTIR), i.e. FTIR absorption spectroscopy. (Note that the IR absorption spectrum can also be easily derived from the transmission spectrum.)

In some embodiments, the scanning probe microscope system includes a scanning probe microscope controller, which refers to a system that facilitates data acquisition and AFM-IR system control. The controller may be a single integrated electronics housing (enclosser) or may include multiple distributed elements. The control element may control the positioning and/or scanning of the probe tip and/or the sample. Data concerning probe deflection, motion, or other responses may also be collected to provide control of radiation source power, polarization, steering, focusing, and/or other functions. The control elements and the like may comprise computer program means or digital logic means and may be implemented using any combination of various 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 other circuit elements. The memory is used to store a computer program and may be executed with discrete circuit components to implement one or more of the processes described herein.

In some embodiments, a "detector" in the context of a detection beam refers to an optical detector that produces 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 other detector technologies that produce a signal indicative of the amount of light incident on the detector surface. The detector may also be a fluorometer and/or a raman spectrometer.

In some embodiments, an "electrochemical tunneling microscope" is any of the following documents. Mo Lijun the nanometer science and technology, electrochemical scanning tunneling microscopy and its application [ M ]. Science Press, 2015. Yan Jiawei, zhan Dongping, mao Bingwei. Scanning probe microscopy and its use in electrochemistry [ J ]. University of mansion, journal of the university of mansion (Nature science edition), 2020 (5).

In some embodiments, an "electrochemical atomic force microscope" is any of the following documents: sun Shigang, et al, electrochemical measurement principles and methods, xiamen university Press, 2021.Cai Shen, guohong Hu, ling-Zhi Cheong, shiqiiang Huang, ji-guard Zhang, deyu Wang, direct Observation of the Growth of Lithium Dendrites on Graphite Anodes by Operando EC-AFM, small Methods,2018,2,1700298.

In some embodiments, the nanoinfrared spectroscopy technique includes the s-SNOM technique performed in IR, which is a useful technique for measuring and mapping optical properties/material composition of some micro-nano resolution surfaces. Various aspects of this technique are described in U.S. applications 13/835,312, 14/322,768, 14/634,859, 14/957,480 and 15/249,433, by the co-inventors of the present application. These applications are incorporated herein by reference in their entirety.

In some embodiments, nanoinfrared spectroscopy techniques include atomic force microscope based infrared analysis system (AFM-IR) techniques, which are useful techniques for measuring and mapping optical properties/material compositions of some surfaces with micro-nano resolution. Various aspects of this technology are described in U.S. patent nos. 8869602, 8680457, 8402819, 8001830, 9134341, 8646319, 8242448 and U.S. patent application nos. 13/135,956 and 15/348,848 to the 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.Dazzi A, prater C B, huQ, et al AFM-IR Combining Atomic Force Microscopy and Infrared Spectroscopy for Nanoscale Chemical Characterization [ J ]. Applied Spectroscopy,2012,66 (12): 1365. These applications are incorporated herein by reference in their entirety.

In some embodiments, the term "infrared-transparent" refers to a transmittance of 50% or more, such as 60% or more, such as 70% or more, such as 80% or more, such as 90-100% or more, for infrared radiation.

Advantageous effects

One or more embodiments of the present disclosure have one or more of the following benefits:

(1) The invention provides a novel electrochemical nano infrared spectrum microscope which can perform nano infrared analysis (such as nano infrared analysis based on photo-thermal expansion or nano infrared analysis based on near-field infrared scattering or nano infrared analysis based on photo-induced force) on a sample to be detected under a controllable potential;

(2) The invention provides a novel electrochemical nano infrared spectrum microscopic analysis method, which can perform nano infrared analysis (such as micro infrared analysis based on photo-thermal expansion or micro infrared analysis based on near-field infrared scattering) on a sample to be detected under a controllable potential;

(3) The invention provides a novel electrochemical nano infrared spectrum microscope, which comprises a novel electrochemical detection cell, wherein the novel electrochemical detection cell is provided with an infrared permeable window, and a sample area is arranged on the inner side surface of the infrared permeable window. Based on the above, the infrared radiation directly irradiates the sample to be measured after passing through the infrared permeable window, and does not need to pass through electrolyte. Therefore, the influence of the electrolyte on infrared radiation is avoided, and the detection precision and sensitivity are improved.

(4) The structure of the infrared permeable window can comprise a total internal reflection prism, infrared radiation is focused on the surface of the prism through the total internal reflection prism and subjected to total internal reflection, and the detection sensitivity is improved.

(5) The infrared permeable window is provided with an infrared permeable current collector in the sample area, and the current collector is electrically connected with the sample to be measured, so that the current of the sample to be measured can be collected better.

(6) The infrared permeable current collector is provided with a surface plasmon array structure, and the structural design realizes the further enhancement of an infrared radiation electric field in a local range, so that the detection sensitivity is improved.

Drawings

FIG. 1 shows a schematic diagram of an electrochemical nanoinfrared spectroscopy microscope of some embodiments.

Figure 2 shows a schematic diagram of an electrochemical nanoinfrared spectroscopy microscope of yet other embodiments.

FIG. 3 shows a schematic diagram of an electrochemical detection cell of an electrochemical nanoinfrared spectroscopy microscope in accordance with still other embodiments.

FIG. 4 shows a schematic diagram of an electrochemical detection cell of an electrochemical nanoinfrared spectroscopy microscope of yet other embodiments.

FIG. 5 shows a partial schematic view of an electrochemical detection cell of an electrochemical nanoinfrared spectroscopy microscope of yet other embodiments.

FIG. 6 (a) shows CV curves obtained by cyclic voltammetric scanning detection of a sample to be tested with a counter electrode; fig. 6 (b) shows an electroless nano infrared spectrum, an infrared spectrum at a potential of-0.25V, an infrared spectrum at a potential of 0.25V of a sample to be measured. The samples showed a change in the overall intensity for infrared light absorption. Fig. 6 (c) shows an infrared imaging diagram of the sample to be measured at a potential of-0.25V. Fig. 6 (d) shows an infrared imaging diagram of the sample to be measured at a potential of-0.25V.

Fig. 7 (a) shows a schematic diagram of an electrochemical nanoinfrared spectroscopy microscope of some embodiments. Fig. 7 (b) shows AFM scan imaging of surface structure features of a 10nm gold film by a scanning probe. Fig. 7 (c) shows AFM scan imaging of PNTP modified gold film surface structure features by a scanning probe. Fig. 7 (d) shows CV curves of cyclic voltammetric scans performed on the original gold film and PNTP-modified gold film. Fig. 7 (e) shows an infrared spectrum after cyclic voltammetry scanning for each week. FIG. 7 (f) shows the characteristic wavenumber (1505 cm ^-1 ) And (5) scanning and imaging the obtained nanometer infrared spectrum. FIG. 7 (g) shows the characteristic wavenumber (1594 cm ^-1 ) And (5) nanometer infrared spectrum scanning imaging obtained by the characteristic wave number.

Fig. 8 (a) shows a schematic diagram of an electrochemical nanoinfrared spectroscopy microscope of some embodiments. Fig. 8 (b) and (c) show photographs of an initial gold film and a PANI-deposited gold film, respectively. Fig. 8 (d) shows a CV curve of cyclic voltammetry scans for each week. FIG. 8 (e) shows the performance of cyclic voltammetry scans on gold film, BAF ₂ And respectively performing infrared spectrum curves obtained by infrared spectrum scanning. Fig. 8 (f) shows an AFM scan image of a gold film deposited with PANI after 8 cyclic voltammetric scans. Fig. 8 (g) shows the nano-infrared spectral scanning imaging of the sample after the 8 th week of scanning.

Detailed Description

Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are performed according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.

FIG. 1 shows a schematic diagram of an electrochemical nanoinfrared spectroscopy microscope (EC-nanoIR) of some embodiments. FIG. 2 shows a schematic diagram of an electrochemical nanoinfrared spectroscopy microscope (EC-nanoIR) of yet other embodiments. FIG. 3 shows a partial schematic view of an electrochemical detection cell of an electrochemical nanoinfrared spectroscopy microscope (EC-nanoIR) of yet other embodiments. As shown in fig. 1 to 3:

in some embodiments, fig. 1 shows an electrochemical nanoinfrared spectroscopy microscope (EC-nanoIR) comprising:

an electrochemical detection cell 10, the electrochemical detection cell 10 comprising: the detection chamber 11 and a wall 12 surrounding the detection chamber, wherein the wall 12 comprises an infrared permeable window 121, a sample area 123 is arranged on the inner side surface of the infrared permeable window 121, and the sample area 123 is used for placing a sample 13 to be detected;

A scanning probe microscope system 20, the scanning probe microscope system 20 being configured to interact with a sample 13 to be measured located in a sample area 123 by means of a scanning probe 21 and to measure a response of the scanning probe 21;

an infrared radiation source 30, said infrared radiation source 30 being configured to emit infrared radiation 32 from an outer side of said infrared transparent window 121 towards said sample area 123.

In the novel electrochemical nano infrared spectrum microscope, the novel electrochemical nano infrared spectrum microscope comprises a novel electrochemical detection cell 10, wherein the novel electrochemical detection cell 10 is provided with an infrared permeable window 121, and a sample area 123 is arranged on the inner side surface of the infrared permeable window 121. Based on this, the infrared radiation 32 passes through the infrared-transparent window 121 and then directly irradiates the sample 13 to be measured without passing through the electrolyte. Therefore, the influence of the electrolyte on infrared radiation is avoided, and the detection precision and sensitivity are improved.

In one embodiment, the scanning probe microscope system is a scanning tunneling microscope system or an atomic force microscope system.

In one embodiment, the scanning probe microscope system is an atomic force microscope system that extracts an absorption signal from a contact resonance with a scanning probe as the sample expands or contracts, the expansion or contraction being caused by infrared radiation in a sample region;

Preferably, the electrochemical nano-infrared spectroscopy microscope comprises an atomic force microscope based infrared analysis system (AFM-IR) that performs an analysis with the infrared radiation source 30 through the scanning probe microscope system 20.

In one embodiment, the electrochemical nanoinfrared spectroscopy microscope further comprises a scattered light detector that collects scattered light emanating from the sample region, the scattered light being caused by the sample region being subjected to infrared radiation;

in one embodiment, the electrochemical nano-infrared spectroscopic microscope comprises a scattering scanning near field optical microscope (s-SNOM) that performs an analysis with the infrared radiation source 30 through the scanning probe microscope system 20.

As shown in fig. 2, in one embodiment, the electrochemical nanoinfrared spectrum microscope further comprises a first driving device 51, and the first driving device 51 drives the electrochemical detection cell to move.

In one embodiment, the electrochemical nanoinfrared spectrum microscope further comprises a second driving means 52, said second driving means 52 driving the focusing mirror 34 for movement, said focusing mirror 34 being adapted for movement of the infrared radiation source.

In one embodiment, the infrared-transparent window 121 is located at the bottom of the electrochemical detection cell 10.

In one embodiment, the electrochemical detection cell 10 includes a wall 12 including a window frame 122, and the infrared-transparent window 121 is removably and sealingly coupled to the window frame 122.

In one embodiment, the infrared-transparent window 121 is made of an infrared-transparent material.

As shown in fig. 3, in one embodiment, the electrochemical nanoinfrared spectroscopy microscope further comprises an electrochemical workstation comprising:

a first working electrode terminal 41, wherein the first working electrode terminal 41 is electrically connected with the sample 13 to be measured in the sample area;

a reference electrode terminal 43, the reference electrode terminal 43 being electrically connected to a reference electrode 143 located in the electrochemical detection cell; and

a counter electrode terminal 44, the counter electrode terminal 44 being electrically connected to a counter electrode 144 located in the electrochemical detection cell.

In one embodiment, the electrochemical workstation further comprises:

and a second working electrode terminal 42, the second working electrode terminal 42 being electrically connected to the scanning probe 21.

In one embodiment, a scanning probe inlet is also provided in the wall 12 of the electrochemical detection cell 10, the scanning probe inlet allowing a scanning probe 21 to extend into the chamber 12.

In one embodiment, scanning probe microscope system 20 includes a scanning probe 21 and a scanning probe deflection detection assembly 22.

In one embodiment, the scanning probe deflection detection assembly 22 includes:

a positioning laser 221 for emitting positioning laser light to the scanning probe;

a position sensitive detector 222 for receiving reflected light of the positioning laser on the scanning probe. The position sensitive detector 222 is a photoelectric device sensitive to the position of the incident light spot on the light sensitive surface, i.e. when the incident light spot falls on different positions of the light sensitive surface of the device, different electric signals are correspondingly output.

In one embodiment, 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 spot on the photosurface of the position sensitive detector 222.

In one embodiment, the infrared radiation source 30 is an infrared laser.

In one embodiment, the infrared radiation source 30 is an infrared pulsed laser.

In one embodiment, the infrared radiation source 30 is a mid-infrared laser.

In one embodiment, the infrared radiation source 30 is a quantum cascade laser.

In one embodiment, the surface of the scanning probe is coated with a conductive layer.

In one embodiment, the material of the conductive layer comprises a metal.

In one embodiment, the material of the conductive layer includes one or more of the following: gold, platinum.

As shown in fig. 4, in some embodiments, infrared-transparent window 121 includes a condenser 124 (e.g., a total internal reflection prism). Based on this scheme, the infrared radiation 31 acts on the sample 13 to be measured through the condenser 124, and the condenser 124 can focus the infrared radiation on the sample 13 to be measured, thereby improving the detection sensitivity.

As shown in fig. 5, in some embodiments, an infrared-transparent current collector 125 is disposed on the sample area 123 of the infrared-transparent window 121. Based on this scheme, an infrared-transparent current collector 125 is used for placing the sample 13 to be measured. Based on this scheme, the infrared-transparent current collector 125 can establish a good electrical connection with the sample 13 to be measured, and does not block the infrared radiation 32 directed to the sample 13 to be measured. The infrared-transparent current collector 125 may 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 measured.

In some embodiments, the present application provides a method of sample analysis comprising

the electrolyte and the sample 13 to be tested are disposed in the sample area 123 of the electrochemical detection cell 10, and the following operations are performed:

control the sample 13 to be measured and the counter electrode 144 to be at a preset potential, control the infrared radiation 32 to be kept at a preset infrared wavelength (for example, infrared characteristic wavelength), control the scanning probe 21 to perform position scanning on the surface of the sample 13 to be measured, keep the infrared radiation 32 irradiated on the interaction area between the scanning probe 21 and the sample 13 to be measured, collect the response signal of the scanning probe 21, and output imaging data based on the change of the response signal with the position.

the electrolyte and the sample 13 to be tested are arranged in the sample area 123 of the electrochemical detection cell 10, and any one of the following operations is performed:

-determining the activity potential: performing cyclic voltammetry scanning between the sample 13 to be detected and the counter electrode 144 to obtain an active potential;

-acquiring an infrared spectrum: controlling the scanning probe 21 and the counter electrode 144 to be at active potential, keeping the infrared radiation 32 irradiated on the interaction area of the scanning probe 21 and the sample 13 to be tested, controlling the infrared radiation 32 to perform wavelength scanning, collecting a response signal of the scanning probe 21, and outputting a nanometer infrared spectrum based on the change of the response signal along with the wavelength of the infrared radiation;

control the sample 13 to be measured and the counter electrode 144 to be at a preset potential (for example, an active potential), control the infrared radiation 32 to be kept at an infrared characteristic wavelength, control the scanning probe 21 to perform a position scanning on the surface of the sample 13 to be measured, keep the infrared radiation 32 irradiated on the interaction area between the scanning probe 21 and the sample 13 to be measured, collect the response signal of the scanning probe 21, and output imaging data based on the change of the response signal with the position.

In some embodiments, a method of sample analysis is provided, comprising

control the scanning probe 21 and the sample 13 to be measured at a preset potential, control the infrared radiation 32 to be kept at a preset infrared wavelength (for example, infrared characteristic wavelength), control the scanning probe 21 to perform position scanning on the surface of the sample 13 to be measured, keep the infrared radiation 32 irradiated on the interaction area of the scanning probe 21 and the sample 13 to be measured, collect the response signal of the scanning probe 21, and output imaging data based on the change of the response signal along with the position.

In some embodiments, the infrared characteristic wavelength may be one or more infrared characteristic absorption wavelengths, i.e., wavelength locations corresponding to infrared characteristic absorption peaks.

In some embodiments, a method of sample analysis is provided, comprising

providing an electrolyte and a sample 13 to be tested in a sample area 123 of the electrochemical detection cell 10;

any one of the following operations is performed:

-determining active sites: controlling the sample 13 to be tested and the scanning probe 21 to be in active potential, and then controlling the scanning probe 21 to perform position scanning on the surface of the sample 13 to be tested;

-acquiring an infrared spectrum: maintaining the irradiation of the infrared radiation 32 on the interaction area of the scanning probe 21 and the sample 13 to be detected, controlling the infrared radiation 32 to perform wavelength scanning, collecting a response signal of the scanning probe 21, and outputting a nanometer infrared spectrum based on the change of the response signal along with the wavelength of the infrared radiation;

Control the scanning probe 21 and the sample 13 to be tested at a preset potential (for example, an active potential), control the infrared radiation 32 to be kept at an infrared characteristic wavelength, control the scanning probe 21 to perform position scanning on the surface of the sample 13 to be tested, keep the infrared radiation 32 irradiated on the interaction area of the scanning probe 21 and the sample 13 to be tested, collect the response signal of the scanning probe 21, and output imaging data based on the change of the response signal along with the position.

The following describes, by way of specific examples, the analysis of a sample to be tested using the electrochemical nanoinfrared spectroscopy microscope described above:

analysis mode 1: electrochemical nanoinfrared spectroscopy at active potential (nanoinfrared spectroscopy may be referred to simply as nanoIR spectroscopy).

The electrochemical workstation 40 controls the potential of the reference electrode 143, scans the potential of the sample 13 to be measured relative to the counter electrode 144, and simultaneously measures the current of the sample 13 to be measured, obtains the cyclic voltammogram of the sample 13 to be measured in the electrolyte, and determines the electrochemical activity potential.

The sample 13 to be measured is then kept at an active potential with respect to the potential of the counter electrode 144, and the surface of the sample 13 to be measured is scanned at the position of the scanning probe 21 while keeping the focus spot of the infrared radiation 32 overlapping the tip of the scanning probe 21. The infrared radiation 32 outputs an infrared light pulse, and the position of the deflected light reflected from the back surface of the cantilever of the scanning probe 21 changes in response to the infrared light pulse. And extracting a position signal of the change of the deflection light, carrying out Fourier transformation, and extracting the amplitude intensity. The infrared radiation 32 is controlled to perform wavelength scanning, so as to obtain the amplitude intensity of the position signal after Fourier transformation of the variation of the polarized light at each wavelength, the excitation wavelength is taken as an abscissa, the amplitude intensity is taken as an ordinate, and the obtained curve is the nanometer infrared spectrum of the surface of the sample 13 to be measured under the active potential.

Techniques for obtaining nanoinfrared spectra can be found in the following document, "Nanoscale simultaneous chemical and mechanical imaging via peak force infared microscopy" l.wang, h.wang, et al science Advances (2017), which is incorporated herein in its entirety.

The potential of the sample 13 to be measured relative to the counter electrode 144 is changed, and the infrared spectrum is repeatedly collected, so that a series of nanometer infrared spectrums on the surface of the sample 13 to be measured under the potential dependence can be obtained.

Further selecting specific infrared characteristic wavelength in the nanometer infrared spectrum as infrared light for exciting the scanning probe 21, extracting position signals of variation of polarized light, and obtaining amplitude intensity after Fourier transformation. Scanning is performed on the surface of the sample 13 to be detected by using a scanning probe 21, so as to obtain the amplitude intensity distribution of a set scanning area on the surface of the sample 13 to be detected, and then the chemical distribution of a certain species under the active potential can be obtained.

Analysis mode 2: scanning electrochemical nanometer infrared spectrum.

(1) Determination of electrochemical Activity potential

And performing cyclic voltammetry scanning between the sample 13 to be detected and the counter electrode 144 to obtain cyclic voltammetry curves of the surface of the sample 13 to be detected, and further determining electrochemical activity potential.

(2) Determination of active sites (regions) on sample surface

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. Scanning the surface of the sample 13 to be detected at the position of the scanning probe 21, recording the current of the scanning probe 21, and plotting the current of the scanning probe 21 with the position to obtain the spatial distribution of the active sites (areas) on the surface of the sample electrode 13.

(3) Determination of the nanoinfrared spectrum at the active site (region)

The scanning probe 21 is controlled to be positioned at an active site (region) on the surface of the sample 13 to be measured, keeping the focused spot of infrared radiation 32 coincident with the tip of the scanning probe 21. The infrared radiation source 30 is controlled to emit pulses of infrared light. The four-quadrant photodetector 222 collects a response position signal generated by the polarized light reflected by the back surface of the cantilever of the scanning probe 21, performs fourier transform on the response signal to obtain an amplitude intensity of the response of the scanning probe 21 at the wavelength, and defines the amplitude intensity as an infrared light signal at the current infrared light wavelength. The infrared radiation 32 is controlled to perform a wavelength sweep to obtain the nanoinfrared spectrum of the scanning probe 12 at the current active site (region).

In addition, potential scanning can be performed between the sample 13 to be detected and the counter electrode 144, and a nanometer infrared spectrum is acquired at each potential to obtain the change information of the intermediate species at the active site in the potential change process.

(4) Obtaining infrared imaging

And selecting infrared characteristic wavelength corresponding to the infrared characteristic peak position in the nanometer infrared spectrum, and then controlling the wavelength of the infrared radiation 32 to be the infrared characteristic wavelength. 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 detected, and infrared imaging of the active site (region) on the surface of the sample 13 to be detected is obtained under the condition of characteristic wavelength and preset potential.

Analytical example 1:

the poly 3-hexylthiophene (P3 HT) is used as a sample to be detected, and the electrochemical nanometer infrared spectrum microscope is adopted to analyze and detect the sample to be detected.

In the analytical detection process, cyclic voltammetry is first performed on the sample to be detected and the counter electrode. Fig. 6 (a) shows a CV curve obtained by cyclic voltammetry scanning detection of a sample to be measured and a counter electrode. According to the cyclic voltammetry scanning result, the active potential of the sample to be detected can be known to be-0.25V and 0.25V respectively.

Then, infrared spectrum detection is carried out on the sample to be detected under the conditions of 0V potential (initial state of the sample), 0.25V potential and 0.25V potential respectively, and the infrared characteristic peak and the characteristic wave number corresponding to the infrared characteristic peak are obtained. Fig. 6 (b) shows an electroless nano infrared spectrum, an infrared spectrum at a potential of-0.25V, an infrared spectrum at a potential of 0.25V of a sample to be measured. The samples showed a change in the overall intensity for infrared light absorption.

Then, respectively carrying out nanometer infrared spectrum scanning imaging on the sample to be detected at-0.25V potential and 0.25V potential. Fig. 6 (c) shows an infrared imaging diagram of the sample to be measured at a potential of-0.25V.

Fig. 6 (d) shows an infrared imaging diagram of the sample to be measured at a potential of-0.25V. The nanometer infrared spectrum scanning imaging refers to carrying out infrared spectrum measurement on each position of a sample to be detected point by point, collecting infrared absorption intensity of each position under a characteristic wave number, endowing different infrared absorption intensities with different colors, and then drawing a position-infrared absorption intensity image, namely an infrared imaging diagram. Comparing fig. 6 (c) and (d), it can be seen that, at the active potential, the refractive index response of the infrared spectrum region of the sample to be measured is significantly changed due to the injection and extraction of electrons.

Analytical example 2:

in the electrolyte (0.1M K) ₂ SO ₄ +0.1M H ₂ SO ₄ ) In the method, nitrobenzene thiophenol (PNTP) is taken as a sample to be detected, and the electrochemical nanometer infrared spectrum display is adoptedThe micro-mirror is used for analyzing and detecting the sample to be detected.

Fig. 7 (a) shows a schematic diagram of an electrochemical nano-infrared spectroscopic microscope. The infrared transparent window 121 is made of BaF ₂ . The infrared-transparent current collector 125 is a gold film having a thickness of 10 nm. An infrared transparent current collector 125 has deposited thereon a self-assembled monolayer of nitrophenol (PNTP SAM). The scanning probe 21 is a silicon (Si) probe.

During analytical detection:

first, a 10nm gold film was subjected to scanning imaging and cyclic voltammetry. Fig. 7 (b) shows AFM scan imaging of surface structure features of a 10nm gold film by a scanning probe. AFM scanning imaging showed that the gold film had a substantially planar surface.

Then, p-nitrophenylthiophenol (PNTP) was used to modify a 10nm gold film. Fig. 7 (c) shows AFM scan imaging of PNTP modified gold film surface structure features by a scanning probe. Comparing fig. 7 (b) and (c), a significant morphology difference was observed, confirming that the gold film surface had been successfully modified by PNTP.

Cyclic voltammetric scanning was performed on the original gold film, and the black curve in fig. 7 (d) shows the CV curve of the 10nm gold film. The CV curve shows substantially no redox peaks.

The p-nitrophenylthiophenol (PNTP) -modified gold film was subjected to cyclic voltammetry (scanning between the infrared-transparent current collector 125 and the counter electrode 144) for 1 to 6 weeks (1 to 6 cycles), and infrared spectroscopic analysis was performed on the sample to be measured after each cyclic voltammetry. Fig. 7 (d) shows a CV curve of each cycle voltammetric scan, and fig. 7 (e) shows an infrared spectrum after each cycle scan. As shown in fig. 7 (d), the current density of the sample surface gradually decreased from week 1 to week 6 as the number of scans increased, which suggests that PNTP was converted into p-aminophenylthiophenol (PATP) by the electrocatalytic reaction during the scan, and the reaction rate gradually decreased as PNTP was consumed. As shown in FIG. 7 (e), as the number of scans increases, the characteristic wavenumber representing the PATP (1594 cm ^-1 ) The corresponding characteristic peak intensity is gradually increased.

The sample after the 6 th week scanning is subjected to nanometer infrared spectrum scanning imaging. The nanometer infrared spectrum scanning imaging refers to carrying out infrared spectrum measurement on each position of a sample to be detected point by point, collecting infrared absorption intensity of each position under a characteristic wave number, endowing different infrared absorption intensities with different colors, and then drawing a position-infrared absorption intensity image, namely an infrared imaging diagram.

FIG. 7 (f) shows the characteristic wave number (1505 cm) ^-1 ) The obtained sample is subjected to nanometer infrared spectrum scanning imaging, and the redder of the image represents the stronger infrared signal. As shown in fig. 7 (f), a part of the positions of the picture appear as red signals, indicating that PNTP exists at these positions; but at the same time, some positions in the picture present signals of other colors, PNTP indicating those positions have been partially or fully converted into PATP.

FIG. 7 (g) shows the characteristic wavenumber (1594 cm ^-1 ) And (3) nanometer infrared spectrum scanning imaging of the sample obtained by the characteristic wave number. The more red the color of the image, the stronger the infrared signal. As shown in fig. 7 (g), a part of the positions of the picture exhibit red signals, indicating that PATPs have been formed at these positions.

Analytical example 3:

the electrochemical nano infrared spectrum microscope adopted by the application is used for observing the polymerization process of ANI into PANI under the action of current.

FIG. 8 (a) shows a schematic diagram of an electrochemical nanoinfrared spectrum microscope, wherein the infrared-transparent window 121 is made of BaF ₂ An infrared-transparent current collector 125 of 10nm gold film, an electrolyte of (0.1. 0.1M H ₂ SO ₄ +30mM ANI). In the above electrolyte, 8 cyclic voltammetric scans were performed between the infrared transparent current collector 125 and the counter electrode 144, and during the scans, ANI was polymerized into PANI by the action of an electric current and deposited on the surface of the infrared transparent current collector 125 (gold film).

Fig. 8 (b) and (c) show photographs of an initial gold film and a PANI-deposited gold film, respectively. The color of the solution and gold film in fig. (c) is darker than in fig. (b), indicating that PANI is formed in the electrolyte and on the gold film surface.

Fig. 8 (d) shows CV curves for cyclic voltammetric scans for each week, as shown by the scan from week 1 to week 8, with increasing number of scans, the current density at the sample surface gradually decreased, indicating that ANI was undergoing polymerization to PANI during the scan, and the reaction rate gradually decreased.

FIG. 8 (e) shows the performance of cyclic voltammetry scans on gold film, BAF ₂ And respectively performing infrared spectrum curves obtained by infrared spectrum scanning. FIG. 8 (e) also shows the IR spectrum of the gold film with PANI deposited after 8 cyclic voltammetry scans, at 1500cm ^-1 The infrared characteristic peaks of (2) confirm that PANI is indeed formed on the surface of the gold film.

Fig. 8 (f) shows an AFM scan image of a gold film deposited with PANI after 8 cyclic voltammetric scans. Fig. 8 (g) shows the nano-infrared spectral scanning imaging of the sample after the 8 th week of scanning. The nanometer infrared spectrum scanning imaging refers to carrying out infrared spectrum measurement on each position of a sample to be detected point by point, collecting infrared absorption intensity of each position under a characteristic wave number, endowing different infrared absorption intensities with different colors, and then drawing a position-infrared absorption intensity image, namely an infrared imaging diagram. The characteristic wavenumber of PANI is 1500cm ^-1 As infrared scan wavenumbers.

As can be seen from comparison of fig. 8 (f) and (g), fig. 8 (f) shows that there are raised structural features (light areas) at part of the positions of the surface of the gold film, confirming that the product is deposited on the surface of the gold film. Fig. 8 (g) shows that the surface of the gold film has characteristic peaks (red areas) corresponding to PANI at partial positions, confirming that PANI is deposited on the surface of the gold film. Comparing fig. 8 (f) and (g) shows that the light-colored region and the red-colored region can substantially coincide, and the two synergistically confirm that the surface of the gold film does form an APNI.

Although specific embodiments of the invention have been described in detail, those skilled in the art will appreciate that: many modifications and variations of the details are possible in light of the above teachings, and such variations are within the scope of the invention. The full scope of the invention is given by the appended claims and any equivalents thereof.

Claims

1. An electrochemical nanoinfrared spectroscopy microscope comprising:

an electrochemical detection cell (10), wherein the electrochemical detection cell (10) comprises a detection cavity (11) and a wall (12) surrounding the detection cavity, the wall (12) comprises an infrared permeable window (121), a sample area (123) is arranged on the inner side surface of the infrared permeable window (121), and the sample area (123) is used for placing a sample (13) to be detected;

a scanning probe microscope system (20), the scanning probe microscope system (20) being configured to interact with a sample (13) to be measured located in a sample zone (123) through a scanning probe (21) and to measure a response of the scanning probe (21);

-an infrared radiation source (30), the infrared radiation source (30) being configured to emit infrared radiation from an outer side of the infrared transparent window (121) towards the sample area (123).

2. The electrochemical nanoinfrared spectroscopy microscope of claim 1, the infrared permeable window (121) comprising a condenser (124).

3. The electrochemical nanoinfrared spectroscopy microscope of claim 2, the condenser (124) being a total internal reflection prism.

4. Electrochemical nanoinfrared spectroscopy microscope according to claim 1, an infrared-transparent current collector (125) being provided on the sample area (123) of the infrared-transparent window (121), the infrared-transparent current collector (125) being used for placing a sample (13) to be measured.

5. The electrochemical nanoinfrared spectroscopic microscope of claim 4, having a surface plasmon array structure disposed on the infrared-transparent current collector (125).

6. The electrochemical nanoinfrared spectroscopy microscope of claim 1, wherein the scanning probe microscope system is a scanning tunneling microscope system or an atomic force microscope system.

7. The electrochemical nanoinfrared spectroscopy microscope of claim 1, wherein the scanning probe microscope system is an atomic force microscope system that extracts an absorption signal from a contact resonance with a scanning probe as the sample expands or contracts, the expansion or contraction being caused by infrared radiation in a sample region;

preferably, the electrochemical nano-infrared spectroscopic microscope comprises an atomic force microscope based infrared analysis system (AFM-IR) performing an analysis with the infrared radiation source (30) by means of the scanning probe microscope system (20).

8. The electrochemical nanoinfrared spectroscopy microscope of claim 1, further comprising a scattered light detector that collects scattered light emanating from the sample region, the scattered light being caused by infrared radiation from the sample region;

preferably, the electrochemical nano-infrared spectroscopic microscope comprises a scattering scanning near field optical microscope (s-SNOM) performing an analysis with the infrared radiation source (30) by means of the scanning probe microscope system (20).

9. The electrochemical nanoinfrared spectroscopy microscope of claim 1, further comprising one or more of:

(1) -first drive means (51), said first drive means (51) driving the movement of said electrochemical detection cell;

(2) -a second driving device (52), said second driving device (52) driving the focusing mirror (34) to move, said focusing mirror (34) being adapted for the movement of the infrared radiation source.

10. Electrochemical nanoinfrared spectroscopic microscope according to claim 1, the infrared permeable window (121) being located at the bottom of the electrochemical detection cell (10).

11. The electrochemical nanoinfrared spectroscopy microscope of claim 1, the electrochemical detection cell (10) comprising a wall (12) comprising a window frame (122), the infrared permeable window (121) being detachably sealed to the window frame (122).

12. Electrochemical nanoinfrared spectroscopy microscope according to claim 1, the infrared permeable window (121) being of infrared permeable material.

13. The electrochemical nanoinfrared spectroscopy microscope of claim 1, further comprising an electrochemical workstation comprising:

a first working electrode terminal (41), wherein the first working electrode terminal (41) is electrically connected with a sample (13) to be detected in a sample area;

a reference electrode terminal (43), the reference electrode terminal (43) being electrically connected to a reference electrode (143) located in the electrochemical detection cell; and

a counter electrode terminal (44), the counter electrode terminal (44) being electrically connected to a counter electrode (144) located in the electrochemical detection cell.

14. The electrochemical nanoinfrared spectroscopy microscope of claim 13, the electrochemical workstation further comprising:

and a second working electrode terminal (42), wherein the second working electrode terminal (42) is electrically connected with the scanning probe (21).

15. Electrochemical nanoinfrared spectroscopy microscope according to claim 1, wherein a scanning probe inlet is further provided in the wall (12) of the electrochemical detection cell (10), said scanning probe inlet being provided for a scanning probe (21) to extend into the chamber (12).

16. The electrochemical nanoinfrared spectroscopy microscope of claim 1, the scanning probe microscope system (20) comprising a scanning probe (21) and a scanning probe deflection detection assembly (22);

Preferably, the scanning probe deflection detection assembly (22) comprises:

a positioning laser (221) for emitting positioning laser light to the scanning probe;

a position sensitive detector (222) for receiving reflected light of the positioning laser on the scanning probe.

17. The electrochemical nanoinfrared spectroscopic microscope of claim 1, the infrared radiation source being an infrared laser;

preferably, the infrared radiation source is an infrared pulsed laser;

preferably, the infrared radiation source is a mid-infrared laser;

preferably, the infrared radiation source is a quantum cascade laser.

18. The electrochemical nanoinfrared spectroscopic microscope of claim 1, the surface of the scanning probe being coated with a conductive layer;

preferably, the material of the conductive layer comprises metal;

19. A sample analysis method includes

Providing an electrochemical nano-infrared spectroscopic microscope of any one of claims 1 to 18;

an electrolyte and a sample (13) to be tested are arranged in a sample area (123) of the electrochemical detection cell (10), and the following operations are performed:

-controlling the sample (13) to be measured and the counter electrode (144) at a predetermined potential, controlling the infrared radiation (32) to be kept at a predetermined infrared wavelength (for example, an infrared characteristic wavelength), controlling the scanning probe (21) to perform a position scanning on the surface of the sample (13) to be measured, keeping the infrared radiation (32) irradiated on the area where the scanning probe (21) interacts with the sample (13) to be measured, collecting a response signal of the scanning probe (21), and outputting imaging data based on a change of the response signal with the position.

20. The method of analyzing a sample according to claim 19, further comprising performing any of the following operations:

-determining the activity potential: performing cyclic voltammetry scanning between a sample (13) to be detected and a counter electrode (144) to obtain an active potential;

-acquiring an infrared spectrum: controlling the scanning probe (21) and the counter electrode (144) to be at active potential, keeping the infrared radiation (32) irradiated on the interaction area of the scanning probe (21) and the sample (13) to be detected, controlling the infrared radiation (32) to perform wavelength scanning, collecting a response signal of the scanning probe (21), and outputting a nanometer infrared spectrum (nanoIR) based on the change of the response signal along with the wavelength of the infrared radiation;

-determining an infrared characteristic wavelength: positioning infrared characteristic peaks from a nanometer infrared spectrum (nanoIR) to determine infrared characteristic wavelengths;

-controlling the sample (13) to be measured and the counter electrode (144) to be at a preset potential (e.g. an active potential), controlling the infrared radiation (32) to be kept at an infrared characteristic wavelength, controlling the scanning probe (21) to perform a position scanning on the surface of the sample (13) to be measured, keeping the infrared radiation (32) irradiated on the area where the scanning probe (21) interacts with the sample (13) to be measured, collecting a response signal of the scanning probe (21), and outputting imaging data based on the change of the response signal with the position.

21. A sample analysis method includes

-providing an electrolyte and a sample (13) to be tested in a sample zone (123) of the electrochemical detection cell (10), performing any one of the following operations:

-controlling the scanning probe (21) at a predetermined potential with respect to the sample (13) to be measured, controlling the infrared radiation (32) to be maintained at a predetermined infrared wavelength (e.g. an infrared characteristic wavelength), controlling the scanning probe (21) to perform a position scanning on the surface of the sample (13) to be measured, maintaining the infrared radiation (32) to irradiate the area where the scanning probe (21) interacts with the sample (13) to be measured, collecting a response signal of the scanning probe (21), and outputting imaging data based on a change of the response signal with the position.

22. The sample analysis method of claim 21, further comprising performing any of the following operations:

-determining active sites: controlling the sample (13) to be detected and the scanning probe (21) to be in active potential, and then controlling the scanning probe (21) to perform position scanning on the surface of the sample (13) to be detected;

-acquiring an infrared spectrum: maintaining the irradiation of infrared radiation (32) on the interaction area of the scanning probe (21) and the sample (13) to be detected, controlling the infrared radiation (32) to perform wavelength scanning, collecting response signals of the scanning probe (21), and outputting nanometer infrared spectrum (nanoIR) based on the change of the response signals along with the wavelength of the infrared radiation;

-controlling the scanning probe (21) and the sample (13) to be at a preset potential (e.g. an active potential), controlling the infrared radiation (32) to be kept at an infrared characteristic wavelength, controlling the scanning probe (21) to perform a position scanning on the surface of the sample (13), keeping the infrared radiation (32) irradiated on the area where the scanning probe (21) interacts with the sample (13), collecting a response signal of the scanning probe (21), and outputting imaging data based on the change of the response signal with the position.