CN-122016693-A - Multi-reactant catalytic intermediate tracing and dynamic decoupling method

CN122016693ACN 122016693 ACN122016693 ACN 122016693ACN-122016693-A

Abstract

The invention discloses a multi-reactant catalytic intermediate tracing and dynamic decoupling method which comprises the steps of constructing a multi-reactant phase sensitive detection in-situ infrared online test system, designing concentration change modes of different periods for reactants, periodically changing the concentration of the reactants after starting detection, collecting infrared spectrum data of sampling time points and calculating the concentration of the reactants, converting a detection result into a phase dependent conversion result and an absorbance conversion result, determining characteristic wave numbers of a plurality of candidate intermediates and reaction main products, extracting the phase dependent absorbance from the absorbance conversion result of the reactants according to the characteristic wave numbers, calculating the maximum intensity of the candidate intermediates and the phase difference between the absorbance conversion result and the corresponding reactant concentration conversion result, obtaining calculation results of the candidate intermediates and the reaction main products, and carrying out intermediate source, main-auxiliary reaction decoupling and intermediate generation sequence analysis.

Inventors

ZHANG HONGNA
HUANG YU

Assignees

中国科学院地球环境研究所

Dates

Publication Date: 20260512
Application Date: 20251230

Claims (10)

1. A multi-reactant catalytic intermediate tracing and kinetic decoupling method, comprising: S1, constructing a multi-reactant phase sensitive detection in-situ infrared online test system; s2, determining a plurality of reactants, and designing concentration change modes with different periods for each reactant; S3, based on the system, starting detection after background spectrum data acquisition is completed, enabling each reactant concentration to periodically change according to respective concentration change modes, collecting infrared spectrum data of each sampling time point, including absorbance corresponding to wave numbers, and calculating reactant concentrations corresponding to each sampling time point to obtain detection results after a plurality of period changes; S4, converting the detection result from time dependence to phase dependence to obtain a concentration conversion result of each reactant and an absorbance conversion result of each reactant; S5, determining the characteristic wave numbers of the candidate intermediates and the reaction main products, extracting the phase-dependent absorbance at the characteristic wave number from the absorbance conversion results of each reactant for each characteristic wave number, calculating the maximum intensity and the phase difference between the maximum intensity and the corresponding reactant concentration conversion result, and forming the calculation result of the characteristic wave number together, so as to obtain the calculation result of each candidate intermediate and the reaction main product; And S6, performing intermediate source analysis, main and side reaction decoupling analysis and intermediate generation sequence analysis based on calculation results of each candidate intermediate and the reaction main product.
2. The method of claim 1, wherein the multi-reactant phase-sensitive detection in-situ infrared online test system comprises: the system comprises an in-situ infrared spectrum acquisition unit, a reaction unit, a control unit and a data acquisition processing unit, wherein: The in-situ infrared spectrum acquisition unit is used for acquiring time-resolved infrared spectrum data of a reaction interface in real time in the reaction process; the reaction unit is positioned in the in-situ infrared spectrum acquisition unit and is used for accommodating reactants to form a reaction environment; The control unit is used for controlling the concentration of the reactants by controlling the flow of the reactants according to the concentration change modes of different periods of each reactant and realizing the control among systems; the data acquisition processing unit is used for recording time data and spectrum data, calculating concentration data and executing relevant calculation and analysis processing.
3. The method of claim 2, wherein in S2, the concentration variation pattern of different periods is designed for each reactant, comprising: A different periodic waveform function is designed for each reactant to indicate the periodic variation of reactant concentration, wherein the waveform function comprises sine waves, square waves and step waves.
4. The method of claim 3, wherein the step of, The control unit comprises a flow control system, a function waveform generator and a trigger controller; The flow control system comprises flow controllers corresponding to reactants, the function waveform generator is used for generating waveform functions designed in advance for each reactant and outputting the waveform functions to the corresponding flow controllers in the flow control system, so that the flow controllers perform flow control according to the given waveform functions to realize concentration control, and the trigger controller is also used for realizing synchronous work of the in-situ infrared spectrum acquisition unit, the flow control system, the function waveform generator and the data acquisition processing unit.
5. The method of claim 3, wherein the plurality of reactants comprises reactant a and reactant B; S3, obtaining detection results after a plurality of period changes, wherein the process comprises the following steps: after the start of the detection, the concentration of the reactant A is periodically controlled according to the waveform function Periodically varying the concentration of reactant B according to the waveform function Periodically changing, regulating the concentration of inert gas, maintaining a steady state reference state in real time, ; After the start-up detection, synchronizing at a preset sampling interval Collecting each sampling time point And recording each sampling time point And calculating each sampling time point Concentration of the corresponding reactant A Concentration of reactant B Obtaining detection results of reactants after a plurality of periodic changes, wherein, Less than And Each sampling time point The corresponding infrared spectrum data is a wave number And absorbance Is a two-dimensional matrix data of (a) a plurality of data sets.
6. The method of claim 5, wherein S4 comprises: obtaining custom multiple phases , wherein, The range of the values is as follows ; According to the corresponding conversion formula, the concentration of the reactant A in the detection result is calculated Concentration of reactant B And absorbance According to each phase Respectively converting to obtain each phase Under dependence of 、、 And ; Wherein, the corresponding conversion formula includes: ; ; ; ; Wherein, the Conversion result of reactant A concentration; conversion result of reactant B concentration; To take the following measures Absorbance conversion results for the period; To take the following measures Absorbance conversion results for the period; And The period of change of the concentration of the reactant A and the period of change of the concentration of the reactant B are respectively; to detect the expiration time.
7. The method of claim 6, wherein in S5: A process for obtaining a calculation of candidate intermediates, comprising: characteristic wave numbers corresponding to each candidate intermediate From the following Absorbance conversion results for period Is extracted from the characteristic wave number Phase dependent absorbance at And from (a) to (b) Absorbance conversion results for period Is extracted from the characteristic wave number Phase dependent absorbance at ; Calculation of Maximum intensity of (2) A kind of electronic device Maximum intensity of (2) ; Calculation of And reactant A concentration conversion results Is of the phase difference of (2) A kind of electronic device And reactant B concentration conversion results Is of the phase difference of (2) Obtaining each characteristic wave number Data sets of (2) As corresponding intermediates Is calculated according to the calculation result of (2); A process for obtaining a calculation of a reaction main product, comprising: Characteristic wave number corresponding to main product of reaction From the following Absorbance conversion results for period Is extracted from the characteristic wave number Phase dependent absorbance at And from (a) to (b) Absorbance conversion results for period Is extracted from the characteristic wave number Phase dependent absorbance at ; Calculation of Maximum intensity of (2) A kind of electronic device Maximum intensity of (2) ; Calculation of And reactant A concentration conversion results Is of the phase difference of (2) A kind of electronic device And reactant B concentration conversion results Is of the phase difference of (2) Obtaining characteristic wave number Data sets of (2) As the main reaction product Is calculated by the computer.
8. The method of claim 7, wherein in S6, the intermediate source analysis is performed based on the calculation results of each candidate intermediate and the reaction main product, comprising: For each intermediate In the calculation result, if the maximum intensity is Greater than maximum strength And exceeding at least one order of magnitude, determining the intermediate The source of the formation of (a) is reactant A, if the intensity is at maximum Greater than maximum strength And exceeding at least one order of magnitude, determining the source of formation of the intermediate as reactant B, if the maximum strength is And maximum strength Is of the same order, the intermediate is judged The sources of formation of (a) are reactant (A) and reactant (B), thereby obtaining each intermediate Is a result of the source analysis of (a).
9. The method of claim 8, wherein in S6, based on the calculation results of each candidate intermediate and the reaction main product, performing a main-side reaction decoupling analysis includes: For the main reaction product In the calculation result, if the maximum intensity is Greater than maximum strength And exceeds at least one order of magnitude, determining that the primary reaction is biased toward the path where reactant A is dominant, if the maximum intensity Greater than maximum strength And exceeding at least one order of magnitude, determining a path in which the main reaction is biased towards the reactant B, thereby obtaining a main reaction biased path result; For each intermediate If the source analysis result is consistent with the main reaction deflection path result, preliminarily determining the intermediate Is the intermediate of the main reaction channel, otherwise, the intermediate is preliminarily judged Is a side reaction channel intermediate, and the intermediate is obtained A first determination result of the reaction channel source; If the intermediate The source analysis result of (1) is derived from the reactant A, and the phase difference in the calculation result is judged Whether or not to be positioned at If yes, preliminarily determining the intermediate Is a main reaction channel intermediate, if not, the intermediate is preliminarily judged Is a side reaction channel intermediate, and the intermediate is obtained A second determination result of the reaction channel source; If the intermediate The source analysis result of (1) is derived from the reactant B, and the phase difference in the calculated result is judged Whether or not to be positioned at If yes, preliminarily determining the intermediate Is a main reaction channel intermediate, if not, the intermediate is preliminarily judged Is a side reaction channel intermediate, and the intermediate is obtained A second determination result of the reaction channel source; When the intermediate is When the source of the reaction channel is consistent with the source indicated by the first judgment result of the reaction channel source and the second judgment result of the reaction channel source, the intermediate is obtained And (3) obtaining the final judgment result of the reaction channel source of each intermediate, and completing the decoupling analysis of the main and side reactions.
10. The method according to claim 9, wherein in S6, based on the calculation results of each candidate intermediate and the reaction main product, performing intermediate generation sequence analysis includes: If the analysis result of the source of the intermediate is derived from the reactant A, calculating the phase difference corresponding to the reactant A in all intermediate results Sequencing from small to large to represent the sequence of the intermediate generation along the related channels of the reactant A, so as to obtain an intermediate generation sequence analysis result taking the reactant A as a reference; If the analysis result of the source of the intermediate is derived from the reactant B, calculating the phase difference corresponding to the reactant B in all intermediate results Sequencing from small to large to represent the sequence of the intermediate generation along the relevant channels of the reactant B, so as to obtain an intermediate generation sequence analysis result taking the reactant B as a reference.

Description

Multi-reactant catalytic intermediate tracing and dynamic decoupling method Technical Field The invention belongs to the field of catalytic reaction and interface process characterization, and particularly relates to a multi-reactant catalytic intermediate tracing and dynamic decoupling method. Background The catalytic reaction is widely applied to energy conversion and environmental treatment systems, and is an important way for realizing the recycling of greenhouse gases, the efficient removal of organic pollutants and the green synthesis of various chemicals. The development of efficient, stable catalytic systems and catalysts relies on basic research on related interfacial processes, where the tracing of reaction intermediates and their kinetic behavior resolution are the core content of reaction mechanism research. By revealing the generation source, evolution path and coupling relation between the intermediate and each reactant, a real reaction path model can be constructed, and basis is provided for rational design of the catalyst and optimization of a reaction system. At present, the detection of the intermediate mainly relies on in-situ infrared, in-situ Raman, in-situ X-ray absorption, in-situ X-ray photoelectron spectroscopy, in-situ ultraviolet-visible absorption, in-situ fluorescence emission and other spectroscopic techniques, and the intermediate signal is identified from the complex spectrum by combining methods such as difference spectrum, isotope labeling, multivariate statistics and the like, and then the reaction intermediate is tracked from the complex spectrum background by combining chemometric methods such as principal component analysis, multivariate curve resolution and the like. However, the existing method has obvious limitations in terms of signal-to-noise ratio, time resolution and signal decoupling due to low interface intermediate content, short service life and poor stability and high overlap of spectrum signals with reactants and products. Currently, the main technical approaches of the multi-reactant catalysis reaction intermediate tracing and decoupling can be summarized into the following three types, namely an intermediate tracing and signal decoupling method based on in-situ vibration spectrum combined with a chemometric method, an intermediate tracing and decoupling analysis method based on isotope labeling combined with online mass spectrum/chromatography, and the third type of intermediate reaction rate constant determination method of an electrocatalytic and photoelectrocatalytic system, which is proposed by the inventor (CN 119595575A). However, the three methods are difficult to meet the comprehensive requirements of accurate tracing of intermediate sources, effective decoupling of signals and judgment of the generation sequence in an interface catalytic system with multiple reactants. Disclosure of Invention In order to solve the problems in the prior art, the invention provides a multi-reactant catalytic intermediate tracing and dynamic decoupling method. The technical problems to be solved by the invention are realized by the following technical scheme: A multi-reactant catalytic intermediate tracing and kinetic decoupling method comprising: S1, constructing a multi-reactant phase sensitive detection in-situ infrared online test system; s2, determining a plurality of reactants, and designing concentration change modes with different periods for each reactant; S3, based on the system, starting detection after background spectrum data acquisition is completed, enabling each reactant concentration to periodically change according to respective concentration change modes, collecting infrared spectrum data of each sampling time point, including absorbance corresponding to wave numbers, and calculating reactant concentrations corresponding to each sampling time point to obtain detection results after a plurality of period changes; S4, converting the detection result from time dependence to phase dependence to obtain a concentration conversion result of each reactant and an absorbance conversion result of each reactant; S5, determining the characteristic wave numbers of the candidate intermediates and the reaction main products, extracting the phase-dependent absorbance at the characteristic wave number from the absorbance conversion results of each reactant for each characteristic wave number, calculating the maximum intensity and the phase difference between the maximum intensity and the corresponding reactant concentration conversion result, and forming the calculation result of the characteristic wave number together, so as to obtain the calculation result of each candidate intermediate and the reaction main product; And S6, performing intermediate source analysis, main and side reaction decoupling analysis and intermediate generation sequence analysis based on calculation results of each candidate intermediate and the reaction main product. In one embodiment of