Photocatalytic reaction micro-quality detection chip, detection system and detection method

Abstract

The invention discloses a photocatalytic reaction micro-quality detection chip, a detection system and a detection method. The chip comprises a quartz crystal array unit, a non-contact excitation electrode array, a multi-physical field feedback unit and a light-sound combined detection pool, the system integrates an excitation module, an acquisition module, a light source module, a spectrum module and a dynamic compensation module to realize synchronous acquisition of ultraviolet visible, infrared and Raman spectrum and sound wave signals; according to the detection method, a special data analysis algorithm is adopted to process photocatalytic reaction data, the data analysis algorithm takes micro mass as a core variable, a photocatalytic reaction kinetic model is constructed, and environmental interference is dynamically compensated by combining a difference method; according to the invention, the micro-mass change greater than or equal to 100 ng / cm < 2 > (5-10 MHz fundamental frequency) or less than or equal to 10 ng / cm < 2 > (10-20 MHz fundamental frequency) in the photocatalytic reaction can be monitored in the whole process, and the method is suitable for reaction mechanism research and catalyst performance evaluation in the fields of environment purification, energy conversion and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of photocatalytic detection technology, and particularly relates to a photocatalytic reaction micro-mass detection chip, a detection system and a detection method. BACKGROUND

[0002] As an important class of chemical reactions, photocatalytic reactions widely exist in nature and artificial synthetic systems. Typical examples include: photocatalytic degradation of atmospheric pollutants directly affects air quality and climate evolution, photocatalytic decomposition of water to produce hydrogen is a key approach to clean energy production, and photocatalytic degradation of organic pollutants is an effective means of environmental governance. However, such reactions are essentially complex interfacial processes involving synergistic effects of photophysics and photochemistry, and their reaction mechanisms are affected by multiple factors such as concentration, relative humidity, pH value, temperature, light conditions and coexisting substances, resulting in significant limitations in current understanding of their reaction mechanisms.

[0003] In the study of photocatalytic reactions, accurate quantification of reaction parameters (such as reaction concentration, reaction rate, intermediate product generation and conversion, etc.) is crucial. Traditional detection techniques mainly rely on spectroscopic methods to analyze the composition and structure information of reactants or products, but it is difficult to directly establish the correlation between reaction progress and mass change. Although some spectroscopic techniques can indirectly deduce mass change through intensity signals, this process requires complex steps such as standard curve construction, signal normalization and fitting equation, and the results are still not direct mass information in nature.

[0004] As a highly sensitive acoustic detection technology, quartz crystal microbalance (QCM) can directly characterize the mass change at the interface by changes in resonance frequency, and has been widely applied in many fields. However, it faces four key challenges in monitoring photocatalytic reactions:

[0005] Photo-induced multi-physical field coupling interference problem: When light irradiates a traditional QCM sensor, photo-induced thermal effects (resulting in temperature gradients in quartz crystals), photoelastic effects (causing changes in material elastic modulus), and dielectric disturbances (changing dielectric constants) can synergistically cause frequency drifts of tens to hundreds of hertz, far exceeding the signal magnitude of mass detection, making it impossible to separate mass signals from interference signals.

[0006] Lack of in-situ multi-mass reference mechanism: Existing QCM technology lacks independent in-situ reference channels, making it impossible to distinguish between real mass changes and photo-induced disturbances in real time. An ideal system needs to integrate multiple reference modes (blank correction, temperature influence, dark state control, etc.), but traditional QCM only relies on static calibration, which cannot adapt to dynamic reaction environments.

[0007] Optical coupling limitations: The metal electrode on the surface of the quartz crystal of the traditional QCM has significant optical defects: non-transparency hinders light transmission, limiting transmission / back reflection spectrum monitoring; high reflectivity interferes with spectrum reflection measurement.

[0008] Physical and chemical stability defects of metal electrodes: Metal electrodes (such as silver and gold) on the QCM surface are prone to chemical degradation in specific photocatalytic systems (such as silver sulfidation in a sulfur-containing environment), resulting in failure of the quality signal; the mismatch in the thermal expansion coefficients between the electrode and the quartz crystal induces interfacial microcracks under the action of photothermal energy, reducing detection accuracy and possibly damaging the device. Summary of the Invention

[0009] The purpose of the present invention is to solve the technical problems existing in the prior art and to provide a photocatalytic reaction micro-mass detection chip, a detection system and a detection method.

[0010] To achieve the above objectives, the present invention provides a technical solution: a photocatalytic reaction micromass detection chip, the detection chip comprising a chip main control unit, a quartz crystal array unit, a non-contact excitation electrode array unit, a multi-physical field feedback unit, and a photoacoustic detection cell, wherein the quartz crystal array unit, the non-contact excitation electrode array unit, the multi-physical field feedback unit, and the photoacoustic detection cell are all electrically connected to the chip main control unit;

[0011] Quartz crystal array unit: a coplanar array unit composed of n AT-cut circular quartz crystals through a crystal bracket, n ≥ 2, i quartz crystals in the n quartz crystals constitute the reference unit, and the remaining ni quartz crystals constitute the detection unit, 1 ≤ i <n;单个石英晶体厚度为83.5±0.3μm~334±2μm,单个石英晶体的对应基频为20MHz~5MHz;石英晶体通过厚度与基频的对应关系实现光催化反应中不同精度的质量检测;

[0012] The non-contact excitation electrode array unit is formed by n pairs of non-contact excitation electrodes through an electrode bracket. Each pair of non-contact excitation electrodes includes an excitation electrode and a receiving electrode. The corresponding area of ​​the spatial projection of the non-contact excitation electrodes on the quartz crystal surface does not load catalysts and reactants and blocks light transmission. The quartz crystal surface outside the corresponding area can load catalysts and reactants and allow light to pass through.

[0013] The multi-physics field feedback unit integrates a temperature sensor, a stress sensor, a humidity sensor, and a dielectric monitoring module. The multi-physics field feedback unit collects sensor data of temperature, stress, humidity, and dielectric constant in real time, and uses a PID algorithm based on the sensor data to dynamically compensate for environmental interference. The multi-physics field feedback unit is electrically connected to the chip main control unit, and the compensation signal in the dynamic compensation is transmitted to the quartz crystal array unit and the non-contact excitation electrode array unit through the feedback circuit in the chip main control unit.

[0014] The photo-acoustic combined detection pool is provided with at least three optical windows, the material of the optical window is magnesium fluoride or quartz glass, the optical window supports synchronous implementation of ultraviolet-visible absorption spectrum detection with a wavelength of 200-800 nm, infrared spectrum detection with a wavelength of 400-4000 cm -1 , Raman spectrum detection with a wavelength of 1300-1800 cm -1 , and sound signal acquisition; wherein the sound signal acquisition is collected by a collection card and transmitted to a chip main control unit.

[0015] The quartz crystal array unit and the non-contact excitation electrode array unit are installed inside the photo-acoustic combined detection pool, the non-contact excitation electrode array unit is fixed through an insulating support one, and the quartz crystal array unit is vertically fixed above or below the excitation electrode array unit through an insulating support two, forming a closed photocatalytic reaction space.

[0016] The function implementation module: the chip detects the micro-mass of the reactants, catalysts and accompanying substances in the initial, middle and final stages of the photocatalytic reaction through the frequency change of the quartz crystal array unit, combines the spectrum data of the photo-acoustic combined detection pool, calculates the kinetic parameters and thermodynamic parameters with the micro-mass as the core variable, and thus realizes the photocatalytic reaction micro-mass detection.

[0017] Preferably, the corresponding relationship between the thickness and the fundamental frequency of the quartz crystal is that when the thickness of the quartz crystal is 167±1 μm-334±2 μm, that is, the corresponding fundamental frequency is 5 MHz-10 MHz, the quartz crystal is used for detecting the mass change of ≥100 ng / cm 2 in the photocatalytic reaction through the fundamental frequency vibration characteristics of the quartz crystal;

[0018] When the thickness of the quartz crystal is 83.5±0.3 μm-167±1 μm, that is, the corresponding fundamental frequency is 10 MHz-20 MHz, the quartz crystal is used for detecting the mass change of ≤10 ng / cm 2 in the photocatalytic reaction through the sensitivity advantage of the higher fundamental frequency.

[0019] Preferably, in the non-contact excitation electrode array unit, the electrode material is selected from metal (Cu / Ag / Au / Pt), transparent conductive oxide (ITO / FTO / ZTO) or conductive carbon material (carbon / graphite), n pairs of n excitation electrodes and n receiving electrodes of the non-contact excitation electrode correspond to the quartz crystal array unit vertically, the n excitation electrodes and the n receiving electrodes are arranged in parallel above or below the quartz crystal in a non-contact manner through electromagnetic coupling or capacitive coupling principle, to realize excitation and signal reception of the quartz crystal vibration; each pair of non-contact excitation electrodes corresponds to the position of the quartz crystal in the quartz crystal array unit one by one, and the spacing between a single excitation electrode or receiving electrode and the corresponding quartz crystal is 0.1 μm-1 cm.

[0020] Preferably, the side of the photo-acoustic combined detection pool is respectively provided with a gas interface and a liquid interface respectively used for the inlet and outlet of the reaction gas / liquid.

[0021] Preferably, when the photo-acoustic combined detection pool is provided with three optical windows, the three optical windows are respectively an upper optical window, a lower optical window and a side optical window, the upper optical window, the lower optical window and the side optical window correspond to different detection light paths respectively, wherein the upper optical window is used for ultraviolet-visible absorption spectrum detection, the lower optical window is used for infrared spectrum detection, and the side optical window is used for Raman spectrum detection and light incidence of the photocatalytic reaction.

[0022] The application further discloses a photocatalytic reaction micro-quantity detection system, comprising the photocatalytic reaction micro-quantity detection chip.

[0023] The excitation module is an n-channel digital signal generator connected with a band-pass filter, the n-channel digital signal generator is connected with the non-contact excitation electrode array unit through a coaxial cable or a PCB trace, and generates an excitation signal with a specific frequency to excite the quartz crystal to vibrate;

[0024] The acquisition module is an n-channel 24-bit acquisition card connected with a phase-locked frequency counter, the n-channel 24-bit acquisition card acquires the feedback signal of the receiving electrode in the non-contact excitation electrode array unit through a signal amplification circuit, and monitors the frequency change of the quartz crystal in real time;

[0025] The light source module is a tunable light source with a wavelength of 200-800 nm provided with a band-pass filter, the tunable light source provides a catalytic light beam which can be accurately controlled, and then the catalytic light beam is coupled with the optical window on the photo-acoustic combined detection pool through an optical fiber or a lens group, so as to provide energy for the photocatalytic reaction;

[0026] The spectrum module comprises a Fourier transform infrared spectrometer and / or a Raman spectrometer and / or an ultraviolet-visible absorption spectrometer, the spectrum module is connected with the optical window of the photo-acoustic combined detection pool through an optical interface, acquires the spectrum signal in the reaction process, and is used for analyzing the structural change of the reactant, the intermediate product and the catalyst;

[0027] The dynamic compensation module performs PID algorithm on the real-time sensing data of the multi-physical field feedback unit, and dynamically compensates the environmental interference.

[0028] Preferably, in the spectrum module, the ultraviolet-visible absorption spectrometer, the Fourier transform infrared spectrometer and the Raman spectrometer are coupled into the light-acoustic combined detection pool through the first optical path module, the second optical path module and the third optical path module respectively, and the ultraviolet-visible signal, the infrared signal and the Raman signal are coupled into the quartz crystal array unit to realize the synchronous implementation of the ultraviolet-visible absorption spectrum detection with a wavelength of 200-800 nm, the infrared spectrum detection with a wavelength of 400-4000 cm -1 , the Raman spectrum detection with a wavelength of 1300-1800 cm -1 , and the sound signal acquisition, so as to realize the in-situ multi-modal monitoring of the photocatalytic reaction.

[0029] The application further discloses a photocatalytic reaction micro-mass detection method, which comprises the photocatalytic reaction micro-mass detection system.

[0030] (1) reaction precursor stage:

[0031] Mass determination: the frequency difference between the frequency generated by the quartz crystal in the detection unit of the quartz crystal array unit and the frequency generated by the quartz crystal in the reference unit is used to determine the catalyst and initial load mass and the initial adsorption amount of the reactant based on the Sauerbrey equation;

[0032] Structure analysis: the functional groups of the reactant are analyzed by the ultraviolet-visible absorption spectrum or the infrared spectrum or the Raman spectrum of the spectrum module to establish an initial structure baseline;

[0033] (2) reaction process

[0034] Mass monitoring: the change rate of the frequency of the quartz crystal is monitored in real time, the decomposition rate and the cumulative decomposition amount of the reactant are calculated, and the dynamic change of the intermediate product is tracked by fitting the frequency-time curve by solving d(Δm) / dt, the change rate of Δm with time t, through the chemical reaction kinetics and the frequency-mass equation;

[0035] Thermodynamic analysis: the thermodynamic parameters are calculated based on the Arrhenius equation in combination with the data of the multi-physical field feedback unit;

[0036] Structure evolution: the correlation between the mass change and the structure evolution is established by simultaneously tracking the characteristic peaks of the reactant, the characteristic peaks of the intermediate product and the structure change of the catalyst through the in-situ infrared / Raman spectrum;

[0037] (3) reaction termination stage:

[0038] Product quantification: when the rate of frequency change is ≤0.1 Hz / s and the spectral characteristic peaks are stable, it is determined that the reaction is complete, the total amount and distribution ratio of the final product are determined, and mass conservation verification is performed, the mass conservation equation: initial mass = product mass + residual mass + escaped gas mass;

[0039] Structure confirmation: the functional groups of the product and the structure recovery of the catalyst are confirmed by spectral analysis;

[0040] (4) Data integration and report generation

[0041] A quality-structure evolution correlation map is established, and a test report containing the initial reactant mass list, kinetic parameter set, product mass distribution, and structure evolution data is generated.

[0042] Preferably, the detection method uses a special data analysis algorithm to process the data of the photocatalytic reaction, the data analysis algorithm takes micro-mass as the core variable, constructs a photocatalytic reaction kinetics model, dynamically compensates environmental interference by combining the difference method, and constructs a quality-structure evolution correlation map by principal component analysis;

[0043] Dynamic compensation: the detection method specifically uses a special data analysis algorithm to process the data of the photocatalytic reaction, the data analysis algorithm takes micro-mass as the core variable, constructs a photocatalytic reaction kinetics model, dynamically compensates environmental interference by combining the difference method, and constructs a quality-structure evolution correlation map by principal component analysis;

[0044] Dynamic compensation of environmental interference: based on the frequency data of the quartz crystal in the i reference units and the frequency data of the quartz crystal in the detection unit, the difference method is used to eliminate the interference of environmental temperature and stress: Δf detection-Δf reference, the specific algorithm is: through a band-pass filter to separate the environmental interference signal and the mass change signal, use the frequency difference between the frequency of the quartz crystal in the detection unit and the frequency of the quartz crystal in the reference unit as the interference reference, and real-time correct the data of the quartz crystal in the detection unit.

[0045] Preferably, the photocatalytic reaction kinetics model is constructed, including:

[0046] (1) Mass reference and interference deduction algorithm

[0047] Multi-channel reference mechanism: adopt an array mode of "i reference + (n-i) detection" (i≥1), through real-time acquisition of the frequency data of the quartz crystal in the reference unit and the quartz crystal in the detection unit, a dynamic detuning deduction model is established:

[0048] (n-i)Δf mass =f sensor1 (t)+f sensor2 (t)+……f sensorni (t)-f ref1(t)- fref2 (t)-……f refi (t)

[0049] where f sensori (t) is the quartz crystal frequency signal in the detection unit, f ref i(t) is the quartz crystal frequency signal in the reference unit, through which the effects of temperature, stress and other environmental disturbances on the frequency are eliminated, and the precise extraction of micro-mass change is realized;

[0050] Band-pass filtering and noise separation: the environmental disturbance signal and the mass change signal are separated by a second-order Butterworth band-pass filter, and the filter cutoff frequency is dynamically adjusted according to the crystal fundamental frequency;

[0051] (2) Kinetic modeling and equation solving

[0052] Partial differential equation construction: introduce micro-mass Δm as the core variable, and establish the coupled equation of photocatalytic reaction rate and light intensity, reactant concentration:

[0053] In the formula: k1(I) = k10·exp(-αI) is the reaction rate constant induced by light absorption, where k10 is the reference rate constant, α is the light intensity attenuation coefficient, and I is the incident light intensity, unit: mW / cm 2 ; k2 is the product desorption rate constant, which is calculated by the Arrhenius equation k2 = k20·exp(-Ea / RT), where k20 is the pre-exponential factor, Ea is the desorption activation energy, R is the gas constant, and T is the thermodynamic temperature;

[0054] Numerical solution method: the finite difference method is used to discretize the partial differential equation, the time step Δt is set to 0.1-1s, the time step is dynamically adjusted according to the reaction rate, and the spatial grid is divided based on the assumption that the mass distribution on the surface of the quartz crystal is uniform. The change rate dΔm / dt of micro-mass with time is obtained by solving, and the reaction kinetic parameters are further deduced;

[0055] (3) 33-item reaction parameter extraction algorithm

[0056] Reactant parameters:

[0057] Initial coverage and mass of reactants: the initial section of the frequency-time curve is fitted by the Langmuir adsorption model to calculate the initial coverage θ 反应物 and the initial reaction mass M 反应物 of the reactants;

[0058] Thermodynamic parameters of reactants: The adsorption Gibbs free energy ΔGreactant, enthalpy change ΔHreactant and entropy change ΔSreactant of reactants were calculated based on Van't Hoff equation through temperature scanning experiment: lnK = -RΔH·T1+RΔS; wherein K is the adsorption equilibrium constant;

[0059] Kinetic parameters of reactants: The initial adsorption / desorption rate k1 反应物 / k2 反应物 and the maximum adsorption capacity M 反应物max were obtained through frequency-time curve fitting;

[0060] Catalyst parameters:

[0061] Initial coverage and mass of catalyst: The initial coverage θ 催化剂 and initial mass M 催化剂 of catalyst were calculated through the frequency difference before and after catalyst loading;

[0062] Thermodynamic and kinetic parameters of catalyst: The adsorption thermodynamic parameters of catalyst were calculated through in-situ spectrum combined with thermodynamic formula, and the isothermal adsorption kinetic parameters were obtained through adsorption-desorption cycle experiment;

[0063] Accompanying parameters:

[0064] Initial and final parameters of accompanying substances: The initial coverage θ θMixture , initial mass M Mixture of accompanying substances were determined through final frequency change, and the final mass MMixture Final and desorption rate k1 Mixture Final / k2 Mixture Final of accompanying substances were calculated through spectrum analysis;

[0065] Reaction kinetic parameters:

[0066] Photolysis rate: The micro-mass reaction rate kreactant and differential form reaction rate dkreactant / dt of photolysis micro-mass were calculated through micro-mass change rate.

[0067] (4) Mass-structure correlation map construction algorithm

[0068] Data fusion method: The correlation model of quartz crystal micro-mass data and spectral characteristic parameters was established by using partial least squares method, the input variables were micro-mass change Δm, light intensity I and temperature T, the output variables were spectral characteristic peak intensity Ipeak and peak position shift Δν, and the model expression was:

[0069] Ipeak = a0 + a1·Δm + a2·I + a3·T, wherein a0, a1, a2 and a3 are model coefficients, which were determined by cross-validation method;

[0070] Correlation map generation: based on the PLS model, a three-dimensional correlation map of Δm-I-Δν is generated, which intuitively shows the corresponding relationship between quality change and molecular structure evolution, such as the linear correlation between the intensity of the characteristic peak of nitrate at 1380 cm - -1 and the micro-mass loss; R -1 > 0.95. 2 .

[0071] (5) Automatic generation of detection report algorithm

[0072] Data standardization: convert the original data of frequency, spectrum, and environmental parameters into unified units and remove outliers;

[0073] Template report generation: automatically generate a detection report containing the following content according to a preset template:

[0074] Initial parameter list: initial mass of reactants / catalysts, coverage, thermodynamic parameters;

[0075] Kinetic parameter set: k1, k2, activation energy Ea, reaction rate constant;

[0076] Product analysis: product mass distribution, structure characterization data;

[0077] Correlation map: mass-spectrum characteristic peak correlation curve, kinetic fitting curve.

[0078] Advantages of the present application:

[0079] Anti-interference ability is strengthened: through the cooperation of the reference crystal array and the multi-physical field feedback unit, the frequency drift caused by temperature fluctuation (±0.5℃) is suppressed to <0.5Hz, the humidity change (±5%RH) interference is suppressed to <1Hz, and the micro-mass detection precision is ≤10ng / cm 2 .

[0080] Multi-modal detection synergy: simultaneously collect quality signals (quartz crystal) and structure signals (spectrum), and establish a "mass-structure" dynamic correlation model, such as the correlation coefficient of the mass loss rate and the H-O-H bond infrared absorption peak decay rate in the process of photocatalytic decomposition of water, which reaches 0.98.

[0081] High throughput and scalability: the chip array structure supports n≥2 channel parallel detection (such as n=8 can test 8 catalysts at the same time), and the non-contact electrode design is compatible with multiple scene requirements such as photocatalysis, electrocatalysis, and biosensing.

[0082] The present application solves the problems of traditional QCM light-induced interference, light path shielding, and poor electrode stability, and can monitor the photocatalytic reaction of ≥100ng / cm 2 (5-10MHz fundamental frequency) or ≤10ng / cm2 The micro mass variation (10-20MHz base frequency) is suitable for reaction mechanism research and catalyst performance evaluation in the fields of environmental purification and energy conversion. BRIEF DESCRIPTION OF DRAWINGS

[0083] The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:

[0084] Figure 1 is a schematic diagram of a quartz crystal and a quartz crystal array unit of the present application;

[0085] Figure 2 is a schematic diagram of a non-contact electrode and a non-contact electrode array unit of the present application;

[0086] Figure 3 is a schematic diagram of a photocatalytic reaction micro mass detection chip, a quartz crystal and a quartz crystal array unit, a non-contact electrode array unit, and a multi-physical field feedback sensor position of the present application;

[0087] Figure 4 is a schematic diagram of a photocatalytic reaction micro mass detection chip inside a light-sound combined detection pool of the present application;

[0088] Figure 5 is a schematic diagram of a photocatalytic whole-process micro mass detection system of the present application;

[0089] Figure 6 is a schematic diagram of photocatalytic whole-process micro mass curve partition of the present application;

[0090] LIST OF DRAWINGS

[0091] 1-quartz crystal, 2-crystal support, 3-excitation electrode, 4-receiving electrode, 5-electrode support, 6-non-contact excitation electrode array unit, 7-pitch, 8-multi-physical field feedback unit, 9-light-sound combined detection pool, 10-upper optical window, 11-lower optical window, 12-side optical window, 13-gas joint, 14-liquid joint, 15-excitation module, 16-acquisition module, 17-light source module, 18-catalytic light beam, 19-ultraviolet-visible absorption spectrometer, 20-Fourier transform infrared spectrometer, 21-Raman spectrometer, 22-first light path module, 23-second light path module, 24-third light path module, 25-ultraviolet-visible signal, 26-infrared signal, 27-Raman signal, 28-dynamic compensation module. DETAILED DESCRIPTION

[0092] The detailed description will be given to the specific embodiments of the present application, and the preferred embodiments of the present application are shown in the drawings, which serve to supplement the description of the text part of the specification and enable people to intuitively and visually understand each technical feature and the overall technical scheme of the present application, but it cannot be understood as a limitation on the protection scope of the present application.

[0093] With reference to Figures 1-6 , the present application provides a photocatalytic reaction micro-mass detection chip, which comprises a chip master control unit, a quartz crystal array unit, a non-contact excitation electrode array unit 6, a multi-physical field feedback unit 8 and a photo-acoustic combined detection pool 9, the quartz crystal array unit, the non-contact excitation electrode array unit 6, the multi-physical field feedback unit 8 and the photo-acoustic combined detection pool 9 are electrically connected with the chip master control unit;

[0094] The quartz crystal array unit is a coplanar array unit composed of n AT-cut circular quartz crystals 1 through a crystal support 2, n≥2, i quartz crystals 1 in the n quartz crystals 1 constitute a reference unit, and the remaining n-i quartz crystals 1 constitute a detection unit, 1≤i<n; the thickness of a single quartz crystal 1 is 83.5±0.3μm~334±2μm, and the corresponding fundamental frequency of a single quartz crystal 1 is 20MHz~5MHz; the quartz crystal 1 realizes mass detection with different precisions in the photocatalytic reaction through the corresponding relationship between the thickness and the fundamental frequency;

[0095] The non-contact excitation electrode array unit 6 is formed by n pairs of non-contact excitation electrodes through an electrode support 5, each pair of non-contact excitation electrodes includes an excitation electrode 3 and a receiving electrode 4, the corresponding area of the spatial projection of the non-contact excitation electrode on the surface of the quartz crystal 1 does not load catalyst and reactant and blocks light transmission, and the surface of the quartz crystal 1 outside the corresponding area can load catalyst and reactant and allow light transmission;

[0096] The multi-physical field feedback unit 8 integrates a temperature sensor, a stress sensor, a humidity sensor and a dielectric monitoring module, the multi-physical field feedback unit 8 collects sensing data of temperature, stress, humidity and dielectric constant in the environment in real time, and dynamically compensates the environmental interference based on the sensing data by using a PID algorithm; the multi-physical field feedback unit 8 is electrically connected with the chip master control unit, and the compensation signal in the dynamic compensation is transmitted to the quartz crystal array unit and the non-contact excitation electrode array unit 6 through a feedback circuit in the chip master control unit;

[0097] The photo-acoustic combined detection pool 9 is provided with at least three optical windows 10, the material of the optical window 10 is magnesium fluoride or quartz glass, the optical window 10 supports synchronous implementation of ultraviolet-visible absorption spectrum detection with a wavelength of 200-800nm, infrared spectrum detection with a wavelength of 400-4000cm -1 ​-1 Raman spectrum detection and sound signal collection; wherein the sound signal collection is collected by the collection card and transmitted to the chip main control unit;

[0098] The quartz crystal array unit and the non-contact excitation electrode array unit 6 are installed inside the light-sound combined detection pool 9, the non-contact excitation electrode array unit 6 is fixed by the insulating support one, and the quartz crystal array unit is vertically fixed above or below the excitation electrode array unit 6 by the insulating support two, forming a closed photocatalytic reaction space.

[0099] The function implementation module: the chip detects the micro-mass of the reactants, catalysts and accompanying substances in the initial, middle and final stages of the photocatalytic reaction through the frequency change of the quartz crystal array unit, combines the spectral data of the light-sound combined detection pool 9, calculates the kinetic and thermodynamic parameters with micro-mass as the core variable, and realizes the micro-mass detection of the photocatalytic reaction.

[0100] In this embodiment, the quartz crystal 1 has a corresponding relationship between thickness and fundamental frequency: when the thickness of the quartz crystal 1 is 167±1μm~334±2μm, corresponding to the fundamental frequency of 5MHz~10MHz, the quartz crystal 1 is used to detect the mass change of ≥100ng / cm 2 in the photocatalytic reaction through the fundamental frequency vibration characteristics of the quartz crystal 1.

[0101] When the thickness of the quartz crystal 1 is 83.5±0.3μm~167±1μm, corresponding to the fundamental frequency of 10MHz~20MHz, the quartz crystal 1 is used to detect the mass change of ≤10ng / cm 2 in the photocatalytic reaction through the sensitivity advantage of higher fundamental frequency.

[0102] In this embodiment, in the non-contact excitation electrode array unit 6, the electrode material is selected from metal (Cu / Ag / Au / Pt), transparent conductive oxide (ITO / FTO / ZTO) or conductive carbon material (carbon / graphite), n pairs of n excitation electrodes 3 and n receiving electrodes 4 of the non-contact excitation electrode correspond to the quartz crystal array unit vertically, and n excitation electrodes 3 and n receiving electrodes 4 are arranged in parallel above or below the quartz crystal 1 in a non-contact manner through electromagnetic coupling or capacitive coupling principle, to realize excitation and signal reception of the quartz crystal 1 vibration; each pair of non-contact excitation electrodes and the quartz crystal 1 position one-to-one, and the spacing 7 between a single excitation electrode 3 or receiving electrode 4 and the corresponding quartz crystal 1 is 0.1μm-1cm.

[0103] In this embodiment, the side surface of the light-sound combined detection pool 9 is respectively provided with a gas interface 13 and a liquid interface 14 respectively used for the inlet and outlet of the reaction gas / liquid.

[0104] In this embodiment, when three optical windows are arranged on the photo-acoustic combined detection pool 9, the three optical windows are respectively an upper optical window 10, a lower optical window 11 and a side optical window 12, and the upper optical window 10, the lower optical window 11 and the side optical window 12 correspond to different detection light paths respectively, wherein the upper optical window 10 is used for ultraviolet-visible absorption spectrum detection, the lower optical window 11 is used for infrared spectrum detection, and the side optical window 12 is used for Raman spectrum detection and light incidence of photocatalytic reaction.

[0105] The application further discloses a photocatalytic reaction micro-quantity detection system, which comprises the photocatalytic reaction micro-quantity detection chip.

[0106] The excitation module 15 is an n-channel digital signal generator connected with a band-pass filter, the n-channel digital signal generator is connected with the non-contact excitation electrode array unit 6 of the detection chip through a coaxial cable or a PCB wire, and generates an excitation signal with a specific frequency to excite the quartz crystal 1 to vibrate.

[0107] The acquisition module 16 is an n-channel 24-bit acquisition card connected with a phase-locked frequency counter, the n-channel 24-bit acquisition card acquires the feedback signal of the receiving electrode in the non-contact excitation electrode array unit 6 through a signal amplification circuit, and monitors the frequency change of the quartz crystal 1 in real time.

[0108] The light source module 17 is a tunable light source with a wavelength of 200-800 nm and equipped with a band-pass filter, the tunable light source provides a catalytic light beam 18 which can be accurately controlled, and then the catalytic light beam 18 is coupled with the optical window on the photo-acoustic combined detection pool 9 through an optical fiber or a lens group, so as to provide energy for the photocatalytic reaction.

[0109] The spectrum module comprises a Fourier transform infrared spectrometer 20 and / or a Raman spectrometer 21 and / or an ultraviolet-visible absorption spectrometer 19, the spectrum module is connected with the optical window of the photo-acoustic combined detection pool 9 through an optical interface, acquires the spectrum signal in the reaction process, and is used for analyzing the structural changes of reactants, intermediate products and catalysts.

[0110] The dynamic compensation module 28 performs PID algorithm on the real-time sensing data of the multi-physical field feedback unit 8, and dynamically compensates the environmental interference.

[0111] In this embodiment, in the spectrum module, the ultraviolet-visible absorption spectrometer 19, the Fourier transform infrared spectrometer 20 and the Raman spectrometer 21 are respectively coupled into the light-sound combined detection cell 9 through the first light path module 22, the second light path module 23 and the third light path module 24, and the ultraviolet-visible signal 25, the infrared signal 26 and the Raman signal 27 are coupled into the quartz crystal array unit, so that the ultraviolet-visible absorption spectrum detection with a wavelength of 200-800 nm, the infrared spectrum detection with a wavelength of 400-4000 cm -1 , the Raman spectrum detection with a wavelength of 1300-1800 cm -1 and the sound signal acquisition are realized, and the in-situ multi-modal monitoring of the photocatalytic reaction is realized.

[0112] The application further discloses a photocatalytic reaction micro-mass detection method, which comprises the photocatalytic reaction micro-mass detection system.

[0113] (1) reaction precursor stage:

[0114] Mass determination: the frequency difference between the frequency generated by the quartz crystal 1 in the detection unit of the quartz crystal array unit and the frequency generated by the quartz crystal 1 in the reference unit is determined, the initial catalyst and load mass and the initial adsorption amount of the reactant are determined based on the Sauerbrey equation;

[0115] Structure analysis: the functional groups of the reactant are analyzed by the ultraviolet-visible absorption spectrum or the infrared spectrum or the Raman spectrum of the spectrum module, and the initial structure baseline is established;

[0116] (2) reaction process

[0117] Mass monitoring: the change rate of the quartz crystal 1 with time t is obtained by solving d(Δm) / dt through the chemical reaction kinetics and the frequency mass equation, the frequency change of the quartz crystal 1 is monitored in real time, the decomposition rate and the cumulative decomposition amount of the reactant are calculated, and the dynamic change of the intermediate product is tracked through the frequency-time curve fitting;

[0118] Thermodynamic analysis: the thermodynamic parameters are calculated based on the Arrhenius equation combined with the data of the multi-physical field feedback unit 8;

[0119] Structure evolution: the correlation between the mass change and the structure evolution is established by simultaneously tracking the characteristic peaks of the reactant, the characteristic peaks of the intermediate product and the structure change of the catalyst through the in-situ infrared / Raman spectrum;

[0120] (3) reaction termination stage:

[0121] Product quantification: when the rate of frequency change is ≤0.1 Hz / s and the spectral characteristic peaks are stable, it is determined that the reaction is complete, the total amount and distribution ratio of the final product are determined, and mass conservation verification is performed, the mass conservation equation: initial mass = product mass + residual mass + escaped gas mass;

[0122] Structure confirmation: the functional groups of the product and the structure recovery of the catalyst are confirmed by spectral analysis;

[0123] (4) Data integration and report generation

[0124] A quality-structure evolution correlation map is established, and a test report containing the initial reactant mass list, kinetic parameter set, product mass distribution, and structure evolution data is generated.

[0125] Preferably, the detection method uses a special data analysis algorithm to process the data of the photocatalytic reaction, the data analysis algorithm takes micro-mass as the core variable, constructs a photocatalytic reaction kinetics model, dynamically compensates for environmental interference by using the difference method, and constructs a quality-structure evolution correlation map by principal component analysis.

[0126] Dynamic compensation of environmental interference: based on the frequency data of quartz crystal 1 in i reference units and the frequency data of quartz crystal 1 in the detection unit, the difference method is used to eliminate the interference of environmental temperature and stress: Δf detection - Δf reference, the specific algorithm is: through a band-pass filter to separate the environmental interference signal and the mass change signal, use the frequency difference between the frequency of the quartz crystal 1 in the detection unit and the frequency of the quartz crystal 1 in the reference unit as the interference reference, and real-time correct the data of the quartz crystal 1 in the detection unit.

[0127] Further, a photocatalytic reaction kinetics model is constructed, including:

[0128] (1) Mass reference and interference deduction algorithm

[0129] Multi-channel reference mechanism: use an array mode of "i reference + (n-i) detection" (i≥1), by real-time acquisition of the frequency data of the quartz crystal 1 in the reference unit and the quartz crystal 1 in the detection unit, a dynamic detuning deduction model is established:

[0130] (n-i)Δf mass =f sensor1 (t)+f sensor2 (t)+……f sensorni (t)-f ref1 (t)- fref2 (t)-……f refi (t)

[0131] Wherein, f sensori (t) is the frequency signal of the quartz crystal 1 in the detection unit, f refi(t) is the frequency signal of the quartz crystal 1 in the reference unit, and the influence of environmental interference such as temperature and stress on the frequency is eliminated by dynamic detuning to realize accurate extraction of micro-mass change;

[0132] Band-pass filtering and noise separation: the environmental interference signal and the mass change signal are separated by a second-order Butterworth band-pass filter, and the filter cutoff frequency is dynamically adjusted according to the crystal fundamental frequency;

[0133] (2) Kinetic modeling and equation solving

[0134] Partial differential equation construction: introduce micro-mass Δm as the core variable, and establish the coupled equation of photocatalytic reaction rate and light intensity, reactant concentration:

[0135] In the formula: k1(I) = k10·exp(-αI) is the reaction rate constant induced by light absorption, wherein k10 is the reference rate constant, α is the light intensity attenuation coefficient, and I is the incident light intensity, unit: mW / cm 2 ; k2 is the product desorption rate constant, which is calculated by the Arrhenius equation k2 = k20·exp(-Ea / RT), wherein k20 is the pre-exponential factor, Ea is the desorption activation energy, R is the gas constant, and T is the thermodynamic temperature;

[0136] Numerical solution method: the finite difference method is used to discretize the partial differential equation, the time step Δt is set to 0.1-1s, the time step is dynamically adjusted according to the reaction rate, and the spatial grid is divided based on the assumption that the mass distribution on the surface of the quartz crystal is uniform. The change rate dΔm / dt of the micro-mass with time is obtained by solving, and then the reaction kinetic parameters are inversely calculated;

[0137] (3) 33 reaction parameter extraction algorithm

[0138] Reactant parameters:

[0139] Initial coverage and mass of reactant: the initial section of the frequency-time curve is fitted by the Langmuir adsorption model to calculate the initial coverage θ of the reactant 反应物 and the initial reaction mass M 反应物 ;

[0140] Thermodynamic parameters of reactant: through temperature scanning experiment, the adsorption Gibbs free energy ΔG of the reactant, the enthalpy change ΔH of the reactant and the entropy change ΔS of the reactant are calculated based on the Van't Hoff equation: lnK = -RΔH·T1+RΔS; wherein K is the adsorption equilibrium constant;

[0141] Kinetic parameters of reactant: the initial adsorption / desorption rate k1 反应物 / k2 反应物 and the maximum adsorption capacity M反应物max ;

[0142] Catalyst parameters:

[0143] Initial coverage and mass of catalyst: initial coverage θ and mass M of catalyst were calculated by the difference of frequency before and after catalyst loading 催化剂 and initial mass M 催化剂 ;

[0144] Thermodynamic and kinetic parameters of catalyst: adsorption thermodynamic parameters of catalyst were calculated by in-situ spectroscopy combined with thermodynamic formula, and isothermal adsorption kinetic parameters were obtained by adsorption-desorption cycle experiment

[0145] Accompanying parameters:

[0146] Initial and final parameters of accompanying substance: initial coverage θMixture and initial mass M of accompanying substance were determined by final frequency change, and final mass MMixture Final and desorption rate k1 of accompanying substance were calculated by spectroscopy analysis Mixture ; Mixture Final / k2 Mixture Final ;

[0147] Reaction kinetic parameters:

[0148] Photolysis rate: photolysis micro-mass reaction rate kReactant and differential form reaction rate dkReactant / dt were calculated by micro-mass change rate.

[0149] (4) Mass-structure correlation map construction algorithm

[0150] Data fusion method: partial least squares method was used to establish the correlation model of quartz crystal 1 micro-mass data and spectral characteristic parameters, the input variables were micro-mass change Δm, light intensity I, and temperature T, and the output variables were spectral characteristic peak intensity Ipeak and peak position shift Δν, and the model expression was:

[0151] Ipeak=a0+a1·Δm+a2·I+a3·T, where a0, a1, a2, and a3 are model coefficients, which are determined by cross-validation method

[0152] Correlation map generation: based on the PLS model, a three-dimensional correlation map of Δm-I-Δν was generated, which directly showed the corresponding relationship between mass change and molecular structure evolution, such as the linear correlation between the intensity of NO3 - characteristic peak at 1380 cm -1 and micro-mass loss in the nitrate decomposition process; R 2 >0.95.

[0153] (5) Automatic generation of detection report algorithm

[0154] Data standardization: convert raw data of frequency, spectrum, environmental parameters into unified units and remove outliers;

[0155] Template report generation: automatically generate a detection report containing the following contents according to a preset template:

[0156] Initial parameter list: initial mass of reactants / catalyst, coverage, thermodynamic parameters;

[0157] Kinetic parameter set: k1, k2, activation energy Ea, reaction rate constant;

[0158] Product analysis: product mass distribution, structure characterization data;

[0159] Correlation map: mass-spectrum characteristic peak correlation curve, kinetic fitting curve.

[0160] Example 1:

[0161] Preparation and system setup of photocatalytic whole-process micro-mass detection chip (n = 3, i = 1)

[0162] 1. Chip preparation process

[0163] Quartz crystal 1 pretreatment: select 3 AT-cut quartz crystals, 1 quartz crystal in the reference unit with a thickness of 334 ± 2 μm and a fundamental frequency of 5 MHz; 2 quartz crystals in the detection unit with a thickness of 83.5 ± 0.3 μm and a fundamental frequency of 20 MHz, remove surface contaminants by plasma cleaning machine (power 100 W, time 5 min), surface roughness Ra < 1 nm.

[0164] Non-contact electrode preparation: electrode material is copper, electrode shape is semicircular (inner diameter 20 mm, outer diameter 25 mm, thickness 1 mm), fixed on quartz crystal 1 by 100 μm above through insulation support (preferably polytetrafluoroethylene support), forming a capacitive coupling structure.

[0165] Light-sound combined detection pool 9 assembly:

[0166] Light-sound combined detection pool 9 pool body adopts quartz glass material (transmission range 180-2500 nm), processed into a cubic cavity (edge length 50 mm), 1 optical window (size 30 mm x 30 mm, thickness 5 mm) is arranged on the upper, lower and side surfaces respectively;

[0167] Optical path design: xenon lamp light source (200-800 nm) enters through the side window, is turned by a 45° mirror and is vertically irradiated to the chip surface after turning, spot diameter 5 mm, power density 0-500 mW / cm 2Adjustable; Raman spectra were collected in backscattering mode, 532 nm laser (power 50 mW) was focused on the reaction zone through the upper optical window, and the scattered light was introduced into the spectrometer (resolution 1 cm -1 ) through a filter set.

[0168] 2. System integration parameters

[0169] Excitation module 15: 3-channel digital signal generator (AD9850, frequency stability 1 ppm) connected with band-pass filter (passband frequency 5 MHz ± 10 kHz / 20 MHz ± 10 kHz, stopband attenuation > 40 dB);

[0170] Acquisition module 16: 3-channel 24-bit acquisition card (ADS1299, sampling rate 10 kHz) and phase-locked frequency counter (Agilent 53230A, resolution 0.01 Hz);

[0171] Dynamic compensation module 28: PT100 temperature sensor (accuracy ± 0.1 °C), piezoresistive stress sensor (resolution 10 -6 strain) integrated in the multi-physical field feedback unit 8.

[0172] Example 2

[0173] Micro-mass and spectroscopic synergistic detection of photocatalytic degradation of nitrate

[0174] 1. Experimental setup

[0175] Chip loading: The quartz crystal 1 in the detection unit was loaded with P25 titanium dioxide (5 μL, concentration 10 mg / mL) by drop coating, and after drying, 10 μM potassium nitrate aqueous solution (10 μL) was added dropwise; the quartz crystal 1 in the reference unit was only loaded with P25 titanium dioxide (5 μL);

[0176] Environmental conditions: temperature 25 °C (temperature control accuracy ± 0.1 °C), 50% RH humidity gas carried by nitrogen gas (flow rate 50 mL / min);

[0177] Illumination conditions: 365 nm ultraviolet light (power density 100 mW / cm 2 ) irradiation, illumination time 3600 s.

[0178] 2. Detection results and parameter extraction

[0179] Micro-mass change: The micro-mass loss Δm of the nitrate decomposition process was calculated by the reference deduction model to be 0.57 ng / cm 2 , the decomposition rate δ was 2.1%, and the photodegradation rate k was 1.6 × 10 -4 μg / s;

[0180] Spectroscopic analysis: Raman spectrum: initial moment NO3 - Characteristic peak (1380 cm -1 ) intensity 1200 a.u., decreased to 850 a.u. after 3600 s illumination, while NO2 -1 Characteristic peak (320 a.u.) appeared at 1630 cm - ;

[0181] Infrared spectrum: NO3 - Absorption peak (1380 cm -1 ) intensity decayed by 30%, NO2 -1 Absorption peak appeared at 1320 cm - , confirming the photolysis of potassium nitrate to generate nitrite;

[0182] Kinetic parameters: k1=5.2×10 -5 s -1 ·(mW / cm 2 ) -1 , k2=1.8×10 -4 s -1 , reaction activation energy Ea=42.5 kJ / mol.

[0183] 3. Mass-structure correlation analysis

[0184] The PLS algorithm was used to establish the correlation model between the Raman peak intensity (I) and the micro-mass loss (Δm) of NO3 - : I=-1250·Δm+1200 (R2=0.97). This model can directly infer the micro-mass change from the spectral peak intensity, with an error of <3%, providing a new method for rapid detection of photocatalytic reactions

[0185] This technology can be widely applied to:

[0186] Photocatalytic material screening: rapid evaluation of the mass response efficiency of different catalysts through high-throughput chip arrays, such as the detection of the formaldehyde degradation rate of TiO2 / ZnO composite catalysts;

[0187] Environmental pollutant monitoring: real-time monitoring of the mass change during the photocatalytic degradation of atmospheric particulate matter (PM2.5), combined with infrared spectrum analysis of product composition;

[0188] Energy chemical research: in the process of water splitting to produce hydrogen, the hydrogen adsorption / desorption kinetics on the catalyst surface is evaluated through micro-mass monitoring, optimizing the utilization efficiency of photo-generated carriers;

[0189] Material interface reaction mechanism: in situ study of the mass accumulation and structure evolution of carbon species on the catalyst surface during photocatalytic CO2 reduction, providing quantitative basis for mechanism research.

[0190] The above additional technical features can be combined and used in addition to each other by those skilled in the art without conflicts.

[0191] The above merely describes the preferred embodiments of the present application, and any technical solutions with substantially the same means to achieve the same purpose should fall within the protection scope of the present application.

Claims

1. A photocatalytic reaction micromass detection chip, characterized by: The detection chip includes a chip main control unit, a quartz crystal array unit, a non-contact excitation electrode array unit, a multi-physical field feedback unit, and a photoacoustic combined detection cell. The quartz crystal array unit, the non-contact excitation electrode array unit, the multi-physical field feedback unit, and the photoacoustic combined detection cell are all electrically connected to the chip main control unit; Quartz crystal array unit: A coplanar array unit composed of n AT-cut circular quartz crystals through a crystal support, where n≥2. Among the n quartz crystals, i quartz crystals form a reference unit, and the remaining n - i quartz crystals form a detection unit, where 1≤i<n. The thickness of a single quartz crystal is 83.5±0.3μm to 334±2μm, and the corresponding fundamental frequency of a single quartz crystal is 20MHz to 5MHz. The quartz crystal realizes mass detection with different precisions in the photocatalytic reaction through the corresponding relationship between thickness and fundamental frequency; The non-contact excitation electrode array unit is formed by n pairs of non-contact excitation electrodes through an electrode support. Each pair of non-contact excitation electrodes includes an excitation electrode and a receiving electrode. The corresponding area of the spatial projection of the non-contact excitation electrode on the surface of the quartz crystal does not carry a catalyst and reactants and blocks light transmission, while the surface of the quartz crystal outside the corresponding area can carry a catalyst and reactants and allow light transmission; The multi-physical field feedback unit integrates a temperature sensor, a stress sensor, a humidity sensor, and a dielectric monitoring module. The multi-physical field feedback unit dynamically compensates for environmental interference by collecting sensing data of temperature, stress, humidity, and dielectric constant in environmental parameters in real time and using the PID algorithm based on the sensing data. The multi-physical field feedback unit is electrically connected to the chip main control unit, and the compensation signal in the dynamic compensation is transmitted to the quartz crystal array unit and the non-contact excitation electrode array unit through the feedback circuit in the chip main control unit; The photoacoustic detection cell is provided with at least three optical windows. The optical windows are made of magnesium fluoride or quartz glass. The optical windows support the simultaneous implementation of ultraviolet-visible absorption spectrum detection with a wavelength of 200-800nm ​​and a wavelength of 400-4000cm -1 Infrared spectrum detection, wavelength 1300-1800cm -1 Raman spectroscopy detection and acoustic signal acquisition; wherein, the acoustic signal acquisition is collected by an acquisition card and transmitted to the chip main control unit; The quartz crystal array unit and the non-contact excitation electrode array unit are installed inside the photoacoustic combined detection cell. The non-contact excitation electrode array unit is fixed by an insulating support one, and the quartz crystal array unit is vertically fixed above or below the excitation electrode array unit by an insulating support two to form a sealed photocatalytic reaction space; Function implementation module: The chip detects the micro mass of reactants, catalysts, and by-products in the initial, middle, and final stages of the photocatalytic reaction through the frequency change of the quartz crystal array unit, and combines the spectral data of the photoacoustic combined detection cell to calculate the kinetic parameters and thermodynamic parameters with the micro mass as the core variable, so as to realize the micro mass detection of the photocatalytic reaction.

2. The photocatalytic reaction micromass detection chip according to claim 1, characterized in that: The corresponding relationship between the thickness and fundamental frequency of quartz crystal is as follows: when the thickness of quartz crystal is 167±1μm~334±2μm, that is, the corresponding fundamental frequency is 5MHz~10MHz, through the fundamental frequency vibration characteristics of quartz crystal, quartz crystal is used to detect the mass change ≥100ng / cm in the photocatalytic reaction 2 changes in quality; When the thickness of the quartz crystal is 83.5±0.3μm~167±1μm, that is, corresponding to the fundamental frequency of 10MHz~20MHz, the sensitivity advantage of the higher fundamental frequency is that the quartz crystal is used to detect the mass change in the photocatalytic reaction ≤10ng / cm 2 quality changes.

3. The photocatalytic reaction micromass detection chip according to claim 1, characterized in that: In the non-contact excitation electrode array unit, the electrode material is selected from metals, transparent conductive oxides, or conductive carbon materials. The n excitation electrodes and n receiving electrodes of the n pairs of non-contact excitation electrodes are vertically corresponding to the quartz crystal array unit. The n excitation electrodes and n receiving electrodes are arranged in parallel above or below the quartz crystal in a non-contact manner through the principle of electromagnetic coupling or capacitive coupling to realize the excitation and signal reception of the quartz crystal vibration; Each pair of non-contact excitation electrodes corresponds to the position of the quartz crystal in the quartz crystal array unit, and the distance between a single excitation electrode or receiving electrode and the corresponding quartz crystal is 0.1μm - 1cm.

4. The photocatalytic reaction micromass detection chip according to claim 1, characterized in that: The sides of the photoacoustic detection cell are respectively provided with a gas interface and a liquid interface for the introduction and discharge of reaction gas / liquid.

5. The photocatalytic reaction micromass detection chip according to claim 1, characterized in that: When three optical windows are provided on the photoacoustic detection cell, the three optical windows are an upper optical window, a lower optical window and a side optical window, and the upper optical window, the lower optical window and the side optical window correspond to different detection light paths, respectively. The upper optical window is used for ultraviolet-visible absorption spectrum detection, the lower optical window is used for infrared spectrum detection, and the side optical window is used for Raman spectrum detection and light incidence for photocatalytic reaction.

6. A photocatalytic reaction micromass detection system, comprising a photocatalytic reaction micromass detection chip according to any one of claims 1 to 5, characterized in that: The detection system also integrates an excitation module, an acquisition module, a light source module, a spectrum module and a dynamic compensation module; The excitation module is an n-channel digital signal generator connected to a bandpass filter. The n-channel digital signal generator is connected to the non-contact excitation electrode array unit via a coaxial cable or PCB traces to generate an excitation signal of a specific frequency to excite the quartz crystal vibration. The acquisition module is an n-channel 24-bit acquisition card that is phase-locked to a frequency counter. The n-channel 24-bit acquisition card collects feedback signals from the receiving electrodes in the contactless excitation electrode array unit through a signal amplification circuit and monitors the frequency changes of the quartz crystal in real time. The light source module is a tunable light source with a wavelength of 200 to 800 nm equipped with a bandpass filter. The tunable light source provides a precisely controllable catalytic light beam, which is then coupled to the optical window on the photoacoustic detection cell through an optical fiber or lens group to provide energy for the photocatalytic reaction. The spectral module includes a Fourier transform infrared spectrometer and / or a Raman spectrometer and / or an ultraviolet-visible absorption spectrometer. The spectral module is connected to the optical window of the photoacoustic detection cell through an optical interface to collect spectral signals during the reaction process and to analyze the structural changes of reactants, intermediates and catalysts. The dynamic compensation module uses the real-time sensing data of the multi-physics field feedback unit to perform PID algorithm to dynamically compensate for environmental interference.

7. The photocatalytic reaction micromass detection system according to claim 6, characterized in that: In the spectral module, the UV-visible absorption spectrometer, the Fourier transform infrared spectrometer, and the Raman spectrometer respectively couple the UV-visible signal, infrared signal, and Raman signal into the photoacoustic detection cell through the first optical path module, the second optical path module, and the third optical path module, and illuminate the quartz crystal array unit to support the simultaneous implementation of UV-visible absorption spectrum detection with a wavelength of 200-800nm ​​and a wavelength of 400-4000cm -1 Infrared spectrum detection, wavelength 1300-1800cm -1 Raman spectroscopy detection and acoustic signal acquisition enable in situ multimodal monitoring of photocatalytic reactions.

8. A photocatalytic reaction micromass detection method, comprising a photocatalytic reaction micromass detection system according to any one of claims 6-7, characterized in that: The detection method achieves full-cycle monitoring through a quartz crystal array unit and a spectrum module; the specific steps are as follows: (1) Reaction precursor stage: Mass determination: The catalyst and initial loading mass and the initial adsorption amount of the reactant are determined based on the Sauerbrey equation by the frequency difference between the frequency generated by the quartz crystal in the detection unit and the frequency generated by the quartz crystal in the reference unit of the quartz crystal array unit; Structural analysis: Analyze the functional groups of reactants through UV-visible absorption spectroscopy, infrared spectroscopy, or Raman spectroscopy in the spectral module to establish an initial structural baseline; (2) During the reaction Quality monitoring: By solving the chemical reaction kinetics and frequency-mass equation, we can obtain d(Δm) / dt, the rate of change of Δm with time t, monitor the frequency change of the quartz crystal in real time, calculate the decomposition rate and cumulative decomposition amount of the reactants, and track the dynamic changes of the intermediate products through frequency-time curve fitting; Thermodynamic analysis: Combined with multi-physics feedback unit data, thermodynamic parameters are calculated based on the Arrhenius equation; Structural evolution: Simultaneously track the characteristic peaks of reactants, intermediates, and catalyst structures through in situ infrared / Raman spectroscopy to establish a correlation between mass changes and structural evolution; (3) Reaction termination stage: Product quantification: When the frequency change rate is ≤0.1 Hz / s and the spectral characteristic peak is stable, the reaction is determined to be complete. The total amount and distribution ratio of the final product are measured and mass conservation is verified. The mass conservation equation is: initial mass = product mass + residual mass + escaped gas mass; Structural confirmation: Confirm the functional groups of the product and the recovery of the catalyst structure through spectral analysis; (4) Data integration and report generation Establish a mass-structure evolution correlation map and generate a test report containing the initial reactant mass list, kinetic parameter set, product mass distribution and structural evolution data.

9. The method for detecting micromass in a photocatalytic reaction according to claim 8, wherein: The detection method specifically uses a dedicated data analysis algorithm to process the data of the photocatalytic reaction. The data analysis algorithm uses micro-mass as the core variable to construct a photocatalytic reaction kinetic model, combines the differential method to dynamically compensate for environmental interference, and constructs a mass-structure evolution correlation map through principal component analysis. Dynamic compensation for environmental interference: Based on the frequency data of the quartz crystals in i reference units and the frequency data of the quartz crystals in the detection unit, the differential method is used: Δf detection - Δf reference to eliminate the interference of ambient temperature and stress. The specific algorithm is: the environmental interference signal and the mass change signal are separated by a bandpass filter, and the frequency difference between the frequency generated by the quartz crystal of the detection unit and the frequency of the quartz crystal of the reference unit is used as the interference reference to perform real-time correction on the quartz crystal data of the detection unit.

10. The method for detecting micromass in a photocatalytic reaction according to claim 9, wherein: Construct a photocatalytic reaction kinetic model, including: (1) Mass reference and interference subtraction algorithm Multi-channel reference mechanism: Using an "i reference + (ni) detection" array mode (i ≥ 1), a dynamic detuning subtraction model is established by real-time acquisition of frequency data from the reference unit's quartz crystal and the detection unit's quartz crystal: (n-i)Δf mass =f sensor1 (t)+f sensor2 (t)+……f sensorni (t)-f ref1 (t)- fref2 (t)-……f refi (t) Among them, f sensori (t) is the quartz crystal frequency signal of the detection unit, f ref i(t) is the quartz crystal frequency signal of the reference unit. The dynamic detuning subtraction model is used to eliminate the influence of environmental interferences such as temperature and stress on the frequency, thus achieving accurate extraction of micro-mass changes. Bandpass filtering and noise separation: A second-order Butterworth bandpass filter is used to separate environmental interference signals and quality change signals. The filter cutoff frequency is dynamically adjusted according to the crystal fundamental frequency. (2) Dynamic modeling and equation solving Partial differential equation construction: Introducing micromass Δm as the core variable, the coupled equation of photocatalytic reaction rate, light intensity, and reactant concentration is established: Where: k1(I) = k10 exp(-αI) is the reaction rate constant triggered by light absorption, where k10 is the reference rate constant, α is the light intensity attenuation coefficient, and I is the incident light intensity, unit: mW / cm 2 ; k2 is the product desorption rate constant, calculated by the Arrhenius equation k2 = k20 exp(-Ea / RT), where k20 is the pre-exponential factor, Ea is the desorption activation energy, R is the gas constant, and T is the thermodynamic temperature; Numerical solution method: The partial differential equation is discretized using the finite difference method. The time step Δt is set to 0.1 to 1 s and is dynamically adjusted according to the reaction rate. The spatial grid is based on the assumption of uniform mass distribution on the quartz crystal surface. The time rate of change of the micromass dΔm / dt is solved and the reaction kinetic parameters are inferred. (3) 33 reaction parameter extraction algorithms Reactant parameters: Initial coverage and mass of reactants: The initial segment of the frequency-time curve is fitted by the Langmuir adsorption model to calculate the initial coverage of the reactants θ 反应物 and the initial reaction mass M 反应物 ; Thermodynamic parameters of reactants: Through temperature sweep experiments, the adsorption Gibbs free energy ΔGreactant, enthalpy change ΔHreactant, and entropy change ΔSreactant were calculated based on the Van't Hoff equation: lnK = -RΔH·T1 + RΔS; where K is the adsorption equilibrium constant; Kinetic parameters of the reactants: initial adsorption / desorption rate k1 is obtained by frequency-time curve fitting 反应物 / k2 反应物 and maximum adsorption capacity M 反应物max ; Catalyst parameters: Initial coverage and mass of catalyst: The initial coverage θ is calculated by the frequency difference before and after catalyst loading 催化剂 and initial mass M 催化剂 ; Thermodynamic and kinetic parameters of catalysts: The adsorption thermodynamic parameters of catalysts are calculated by combining in-situ spectroscopy with thermodynamic formulas, and the isothermal adsorption kinetic parameters are obtained through adsorption-desorption cycle experiments; Associated parameters: Initial and final parameters of the companion: Determine the initial coverage θMixture and initial mass M of the companion by the final frequency change Mixture , combined with spectral analysis to calculate the final mass of the accompanying product MMixture Final and the desorption rate k1 Mixture Final / k2 Mixture Final ; Reaction kinetic parameters: Photolysis rate: The photolysis micromass reaction rate kreactant and the differential form reaction rate dkreactant / dt are calculated from the micromass change rate. (4) Algorithm for constructing quality-structure correlation graph Data fusion method: The partial least squares method is used to establish a correlation model between quartz crystal micromass data and spectral characteristic parameters. The input variables are micromass change Δm, light intensity I, and temperature T. The output variables are spectral characteristic peak intensity Ipeak and peak position shift Δν. The model expression is: Ipeak=a0+a1·Δm+a2·I+a3·T, where a0, a1, a2, and a3 are model coefficients determined by cross-validation; Correlation map generation: Based on the PLS model, a three-dimensional correlation map of Δm-I-Δν is generated to intuitively show the corresponding relationship between mass change and molecular structure evolution, such as NO3 in the process of nitrate decomposition - Characteristic peak 1380cm -1 The linear correlation between the intensity and micro mass loss; R 2 >0.

95. (5) Automatic generation algorithm for test reports Data standardization: convert the raw data of frequency, spectrum, and environmental parameters into a unified unit and remove outliers; Templated report generation: Automatically generate a test report containing the following content based on the preset template: Initial parameter list: reactant / catalyst initial mass, coverage, thermodynamic parameters; Kinetic parameter set: k1, k2, activation energy Ea, reaction rate constant; Product analysis: product mass distribution and structural characterization data; Correlation map: mass-spectral characteristic peak correlation curve, kinetic fitting curve.

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