A sulfur-resistant hydrogen permeation sensor based on quantum dot fluorescence effect and its application

Abstract

This invention relates to the field of sensor technology, specifically to a sulfur-resistant hydrogen permeation sensor based on quantum dot fluorescence effect and its application. The sensor includes a quantum dot sensing module, a fluorescence detection module, and a signal processing module. The quantum dot sensing module forms Fe-S bonds with the ZnS shell through thiol ligands, blocking the H2S adsorption pathway. The fluorescence detection module detects fluorescence quenching signals based on a modified Stern-Volmer equation and integrates time-resolved fluorescence technology. The signal processing module integrates temperature and pressure compensation algorithms and a Gaussian filtering model to eliminate pipeline vibration noise. Through material-grade sulfur-resistant design and high-sensitivity fluorescence response, this sensor achieves, for the first time, real-time monitoring of hydrogen permeation at 0.1 ppm in sulfur-containing environments, with an H2S tolerance concentration >1000 ppm. Its operating life is extended from <3 months for traditional sensors to 3 years, and its response time is <30 seconds, 60 times shorter than that of electrochemical sensors. The false alarm rate is reduced from 23% to 0.7%, providing an in-situ, real-time early warning method for pipeline hydrogen embrittlement failure.

Description

Technical Field

[0001] This invention relates to the field of sensor technology, and in particular to a sulfur-resistant hydrogen permeation sensor based on quantum dot fluorescence effect and its application. Background Technology

[0002] In the transportation of sulfur-containing natural gas through pipelines, H2S triggers a chain reaction of steel corrosion:

[0003] H₂S + Fe → FeS + 2H₂ + (Acid corrosion), 2H + +2e - → Hydrogen atoms generated from H2 (hydrogen permeation source) permeate into the inner wall of the pipe, causing hydrogen embrittlement, accounting for 34% of pipe failure cases. Traditional detection technologies have significant bottlenecks:

[0004] Ultrasonic testing: requires machine shutdown for scanning, blind zone >15%, and cannot be monitored in real time;

[0005] Electrochemical sensors: Easily poisoned by H2S (lifespan <3 months), requiring weekly calibration;

[0006] Fiber Bragg gratings: can only measure strain and cannot distinguish hydrogen permeation-specific signals;

[0007] Current technological deficiencies

[0008] Sulfur resistance collapse: Traditional Pd membrane sensors fail after 3 months in sulfur-containing environments, and electrochemical probes drift due to H2S interference, requiring frequent calibration;

[0009] Limited detection dimensions: It cannot separate the coupling interference between hydrogen permeation and environmental factors such as temperature, pressure, and mechanical vibration;

[0010] At the material level: there is a lack of sensitive materials that simultaneously meet the requirements of "hydrogen permeation selectivity > 99%, H2S tolerance concentration > 1000 ppm, and operating temperature -20~150℃".

[0011] At the system level: International standards do not cover quantum dot sensing technology, and traditional threshold alarm solutions have a false alarm rate as high as 23%. Summary of the Invention

[0012] The purpose of this invention is to provide a sulfur-resistant hydrogen permeation sensor based on quantum dot fluorescence effect and its application, aiming to achieve long-term, real-time, in-situ monitoring of hydrogen permeation under high sulfur content, high pressure, wide temperature, and strong vibration conditions, to provide early warning of hydrogen embrittlement risks, and to ensure the safety of industrial facilities.

[0013] To achieve the above objectives, in a first aspect, the present invention provides a sulfur-resistant hydrogen permeation sensor based on quantum dot fluorescence effect, comprising a quantum dot sensing module, a fluorescence detection module, and a signal processing module. The quantum dot sensing module forms Fe-S bonds with the ZnS shell through a thiol ligand, blocking the H2S adsorption pathway. The fluorescence detection module detects fluorescence quenching signals based on a modified Stern-Volmer equation and integrates time-resolved fluorescence technology. The signal processing module integrates temperature and pressure compensation algorithms and a Gaussian filtering model to eliminate pipeline vibration noise.

[0014] The quantum dot sensing module incorporates a sulfur resistance stability quantification formula and a surface coverage calculation formula.

[0015] H2S adsorption energy calculation (based on XPS data):

[0016]

[0017] in:

[0018] Adsorption energy of H2S molecules on the surface of quantum dots;

[0019] : Total energy of the system after adsorption onto thiol-modified quantum dots;

[0020] The individual energy of thiol-modified quantum dots;

[0021] The energy of an isolated H2S molecule;

[0022] Thiol modification (Unmodified 0.8 eV) The adsorption energy is significantly increased, effectively blocking the chemisorption of H2S;

[0023] The formula for calculating surface coverage is as follows:

[0024] Langmuir adsorption model:

[0025]

[0026] in:

[0027] H2S coverage on quantum dot surface (0~1, dimensionless).

[0028] Adsorption equilibrium constant (Pa) -1 );

[0029] Partial pressure of H2S gas (Pa);

[0030] The fluorescence detection module incorporates the original Stern-Volmer equation and multi-physics coupling correction.

[0031] The original Stern-Volmer equation:

[0032]

[0033] in:

[0034] Initial fluorescence intensity in a hydrogen-free environment;

[0035] Fluorescence intensity after hydrogen permeation;

[0036] Stern-Volmer quenching constant, characterizing the sensor's sensitivity to hydrogen;

[0037] : Hydrogen concentration in the environment to be tested;

[0038] Multiphysics coupling correction:

[0039] To eliminate the cross-effects of temperature, pressure, and vibration on the fluorescence signal, the quenching constant is modified to be a function of temperature T and pressure P:

[0040]

[0041] in:

[0042] The absolute temperature of the sensor's operating environment, expressed in Kelvin (K).

[0043] Total pressure of the sensor's operating environment, in kPa;

[0044] The effective quenching constant after temperature and pressure compensation is defined by the following formula:

[0045]

[0046] in:

[0047] The baseline quenching constant under standard conditions (T0=298 K, P0=101.325 kPa);

[0048] Temperature compensation function, using the Arrhenius modified form;

[0049] : Pressure compensation function, using a power-law model.

[0050] The temperature compensation function Defined as:

[0051]

[0052] in:

[0053] Activation energy of hydrogen permeation process ;

[0054] Boltzmann constant ;

[0055] Reference temperature: 298K.

[0056] The pressure compensation function Defined as:

[0057]

[0058] in:

[0059] Reference pressure: 101.325 kPa;

[0060] The pressure index, 0.7, was obtained through experimental fitting based on Henry's law.

[0061] Vibration interference filtering (Gaussian model):

[0062]

[0063] in:

[0064] Fluorescence intensity after vibration compensation (au);

[0065] Measured fluorescence intensity (au);

[0066] Real-time vibration acceleration of the sensor's environment, in m / s². 2 ;

[0067] Characteristic vibration threshold When the vibrational acceleration equals this value, the fluorescence intensity correction factor is: .

[0068] Regarding the derivation of the sensitivity limit theory:

[0069] The limit of detection (LOD) for hydrogen by the sensor is determined by both baseline noise and sensitivity. The formula for calculating the LOD is:

[0070]

[0071] in:

[0072] Baseline noise, i.e., fluorescence intensity under hydrogen-free conditions. The standard deviation is [value missing]. The measured baseline noise level is approximately 0.05%. (Expressed in units of fluorescence intensity, au);

[0073] S: The sensitivity of the analytical method in the low concentration region is defined as the derivative of the response quantity with respect to the hydrogen concentration.

[0074] Regarding the verification of signal-to-noise ratio improvement (time-resolved fluorescence technique):

[0075] Time-resolved fluorescence (TRPL) technology effectively suppresses short-lived background noise (such as scattered light and impurity fluorescence) and preserves long-lived quantum dot fluorescence signals through gated acquisition, thereby significantly improving the signal-to-noise ratio (SNR).

[0076] In continuous-wave (CW) mode, the signal-to-noise ratio is SNR. CW After adopting TRPL mode, pulse excitation and delayed acquisition are used, with the bandwidth only turned on during the quantum dot fluorescence decay period. Acquisition gating. Quantum dot fluorescence lifetime. Gating width Under these conditions, the short-lived background is almost completely eliminated, and only the long-lived fluorescence signal of the quantum dots is collected. Limited by photon shot noise, the signal-to-noise ratio improvement factor of the TRPL mode is proportional to the square root of the ratio of signal accumulation time to the effective bandwidth of the noise, as theoretically stated in the formula:

[0077]

[0078] Secondly, the present invention also provides an application of a sulfur-resistant hydrogen permeation sensor based on the quantum dot fluorescence effect, employing the sulfur-resistant hydrogen permeation sensor based on the quantum dot fluorescence effect as described in the first aspect above, including hydrogen monitoring in sulfur-containing natural gas pipelines, hydrogen energy storage tanks, chemical hydrogenation devices, and nuclear power pressure vessels.

[0079] This invention discloses a sulfur-resistant hydrogen permeation sensor based on quantum dot fluorescence effect. The quantum dot sensing module forms Fe-S bonds with the ZnS shell via thiol ligands, blocking the H2S adsorption pathway. The fluorescence detection module detects the fluorescence quenching signal based on a modified Stern-Volmer equation, integrating time-resolved fluorescence technology. The signal processing module integrates temperature and pressure compensation algorithms and a Gaussian filtering model to eliminate pipeline vibration noise. The quantum dot sensing module receives excitation light from the fluorescence detection module, undergoing fluorescence quenching under hydrogen permeation, resulting in a weakened emission fluorescence signal. The fluorescence detection module incorporates an excitation source and a photodetector, employing time-resolved fluorescence (TRPL) technology to collect long-lived quantum dot fluorescence within a set gate window, suppressing background noise, and based on the modified Stern-Volmer equation... The r-equation converts fluorescence intensity changes into electrical signals. The signal processing module receives the electrical signals output by the fluorescence detection module and uses built-in temperature and pressure compensation functions and Gaussian vibration filtering models to correct environmental interference in real time, thereby obtaining accurate hydrogen concentration values ​​and providing over-limit alarm outputs. Through material-level sulfur-resistant design (thiol ligand modification + core-shell structure) and high-sensitivity fluorescence response (modified Stern-Volmer equation + TRPL technology), this sensor achieves real-time monitoring of 0.1 ppm hydrogen permeation in sulfur-containing environments for the first time. It can tolerate H2S concentrations >1000 ppm, extending its working life from <3 months of traditional sensors to 3 years. The response time is <30 seconds, which is 60 times shorter than that of electrochemical sensors, and the false alarm rate is reduced from 23% to 0.7%, providing an in-situ, real-time early warning method for pipeline hydrogen embrittlement failure. Attached Figure Description

[0080] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the accompanying drawings used in the description of the embodiments or the prior art will be briefly introduced below.

[0081] Figure 1 This is a schematic diagram of a sulfur-resistant hydrogen permeation sensor based on quantum dot fluorescence effect provided by the present invention.

[0082] In the diagram: 1-Quantum dot sensing module, 2-Fluorescence detection module, 3-Signal processing module. Detailed Implementation

[0083] The embodiments of the present invention are described in detail below. Examples of the embodiments are shown in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain the present invention, but should not be construed as limiting the present invention.

[0084] Please see Figure 1In a first aspect, the present invention provides a sulfur-resistant hydrogen permeation sensor based on quantum dot fluorescence effect, comprising a quantum dot sensing module 1, a fluorescence detection module 2, and a signal processing module 3. The quantum dot sensing module 1 forms Fe-S bonds with the ZnS shell through a thiol ligand, blocking the H2S adsorption pathway. The fluorescence detection module 2 detects fluorescence quenching signals based on a modified Stern-Volmer equation and integrates time-resolved fluorescence technology. The signal processing module 3 integrates temperature and pressure compensation algorithms and a Gaussian filtering model to eliminate pipeline vibration noise.

[0085] In this embodiment, the quantum dot sensing module 1 forms Fe-S bonds with the ZnS shell through a thiol ligand, blocking the H2S adsorption pathway. The fluorescence detection module 2 detects the fluorescence quenching signal based on a modified Stern-Volmer equation, integrating time-resolved fluorescence technology. The signal processing module 3 integrates temperature and pressure compensation algorithms and a Gaussian filtering model to eliminate pipeline vibration noise. The quantum dot sensing module 1 receives excitation light from the fluorescence detection module 2 and undergoes fluorescence quenching under hydrogen permeation, resulting in a weakened fluorescence signal. The fluorescence detection module 2 has a built-in excitation source and photodetector, and uses time-resolved fluorescence technology (TRPL) to collect the long-lived fluorescence of quantum dots within a set gate window, suppressing background noise, and converting the fluorescence intensity change into an electrical signal based on the modified Stern-Volmer equation. The signal processing module 3 receives the electrical signal output by the fluorescence detection module 2, and uses the built-in temperature and pressure compensation function and Gaussian vibration filtering model to correct environmental interference in real time, thereby obtaining an accurate hydrogen concentration value. At the same time, it provides an over-limit alarm output. Through material-level sulfur-resistant design (thiol ligand modification + core-shell structure) and high-sensitivity fluorescence response (modified Stern-Volmer equation + TRPL technology), this sensor achieves real-time monitoring of 0.1 ppm hydrogen permeation in a sulfur-containing environment for the first time. It can tolerate H2S concentrations >1000 ppm, and its working life is extended from <3 months of traditional sensors to 3 years. The response time is <30 seconds, which is 60 times shorter than that of electrochemical sensors. The false alarm rate is reduced from 23% to 0.7%, providing an in-situ, real-time early warning method for pipeline hydrogen embrittlement failure.

[0086] Furthermore, the quantum dot sensitive module 1 incorporates a quantitative formula for sulfur resistance stability and a surface coverage calculation formula, as described in claim 2. The quantum dot surface is modified with a thiol ligand (such as HS-CH2COOH) to form stable Fe-S bonds with the ZnS shell, increasing the H2S adsorption energy from 0.8 eV to 2.3 eV, thereby maintaining fluorescence stability for over 2000 hours in a 1000 ppm H2S atmosphere with a cross-sensitivity of <0.5%. The core-shell structure optimization uses a CdSe core (2.5 nm) and a ZnS shell (3-5 nm), balancing hydrogen permeation rate and mechanical strength, extending the operating temperature range to -20~150℃.

[0087] The formula for quantifying sulfur resistance stability:

[0088] H2S adsorption energy calculation (based on XPS data):

[0089]

[0090] in:

[0091] Adsorption energy of H2S molecules on the surface of quantum dots;

[0092] : Total energy of the system after adsorption onto thiol-modified quantum dots;

[0093] The individual energy of thiol-modified quantum dots;

[0094] Energy of an isolated H2S molecule.

[0095] Thiol modification (Unmodified 0.8eV) The adsorption energy is significantly increased, effectively blocking the chemisorption of H2S.

[0096] The formula for calculating surface coverage is as follows:

[0097] Langmuir adsorption model:

[0098]

[0099] in:

[0100] H2S coverage on quantum dot surface (0~1, dimensionless).

[0101] Adsorption equilibrium constant (Pa) -1 );

[0102] Partial pressure of H2S gas (Pa).

[0103] At a total pressure of 101.325 kPa, the corresponding partial pressure for H2S concentration of 1000 ppm is: After thiol modification, the experimental fit Substituting into the calculation, we get This indicates that the surface coverage of H2S was effectively suppressed.

[0104] Furthermore, the fluorescence detection module 2 incorporates a modified Stern-Volmer equation and a multiphysics compensation model. (Quenching constant) Up to 10 6 M −1 The sensitivity is 100 times higher than traditional technologies, with a detection limit as low as 0.1 ppm and a response time of <30 seconds. Time-resolved fluorescence (TRPL) technology effectively suppresses short-lived background noise by extracting the fluorescence signal of long-lived quantum dots, achieving a signal-to-noise ratio improvement factor of 20 (corresponding to a signal-to-noise ratio improvement of approximately 13 dB: 2). It can resolve weak fluorescence changes of less than 5%. Temperature compensation accuracy is ±0.5% (traditional ±15%), and pressure compensation accuracy is ±0.3% (traditional ±8%).

[0105] The original Stern-Volmer equation:

[0106]

[0107] in:

[0108] Initial fluorescence intensity in a hydrogen-free environment;

[0109] Fluorescence intensity after hydrogen permeation;

[0110] Stern-Volmer quenching constant, characterizing the sensor's sensitivity to hydrogen;

[0111] : Hydrogen concentration in the environment to be tested.

[0112] Multiphysics coupling correction:

[0113] To eliminate the cross-effects of temperature, pressure, and vibration on the fluorescence signal, the quenching constant is modified to be a function of temperature T and pressure P:

[0114]

[0115] in:

[0116] The absolute temperature of the sensor's operating environment, expressed in Kelvin (K).

[0117] Total pressure of the sensor's operating environment, in kPa;

[0118] The effective quenching constant after temperature and pressure compensation is defined by the following formula:

[0119]

[0120] in:

[0121] The baseline quenching constant under standard conditions (T0=298 K, P0=101.325 kPa);

[0122] Temperature compensation function, using the Arrhenius modified form;

[0123] : Pressure compensation function, using a power-law model.

[0124] The temperature compensation function Defined as:

[0125]

[0126] in:

[0127] Activation energy of hydrogen permeation process ;

[0128] Boltzmann constant ;

[0129] Reference temperature: 298K.

[0130] The pressure compensation function Defined as:

[0131]

[0132] in:

[0133] Reference pressure: 101.325 kPa;

[0134] The pressure index, 0.7, was obtained through experimental fitting based on Henry's law.

[0135] Furthermore, vibration interference filtering employs an independent Gaussian model for post-processing to eliminate the interference of pipeline vibration noise on fluorescence intensity, reducing the false alarm rate from the traditional 23% to 0.7%. Its expression is:

[0136]

[0137] in:

[0138] Fluorescence intensity after vibration compensation (au);

[0139] Measured fluorescence intensity (au);

[0140] Real-time vibration acceleration of the sensor's environment, in m / s². 2 ;

[0141] Characteristic vibration threshold When the vibrational acceleration equals this value, the fluorescence intensity correction factor is: .

[0142] Regarding the derivation of the sensitivity limit theory:

[0143] The limit of detection (LOD) for hydrogen by the sensor is determined by both baseline noise and sensitivity. The formula for calculating the LOD is:

[0144]

[0145] in:

[0146] Baseline noise, i.e., fluorescence intensity under hydrogen-free conditions. The standard deviation is [value missing]. The measured baseline noise level is approximately 0.05%. (Expressed in units of fluorescence intensity, au);

[0147] S: The sensitivity of the analytical method in the low concentration region is defined as the derivative of the response quantity with respect to the hydrogen concentration.

[0148] This sensor uses the Stern-Volmer equation to describe the fluorescence quenching response:

[0149]

[0150] At low hydrogen concentrations, The fluorescence intensity can be approximated as:

[0151]

[0152] This allows us to obtain the sensitivity of fluorescence intensity changes caused by variations in hydrogen concentration:

[0153]

[0154] Will and Substitute into the LOD formula:

[0155]

[0156] The Stern-Volmer quenching constant of this sensor was experimentally measured. (Expressed in terms of the molar concentration of hydrogen), therefore:

[0157]

[0158] To correlate the detection limit with the volumetric concentration (ppm) in the gaseous environment, unit conversion is required. Under typical sensor operating conditions (total pressure P≈101.325 kPa, temperature T≈298 K), according to the ideal gas law:

[0159]

[0160] in The partial pressure of hydrogen corresponding to a volume fraction of 1 ppm is: 1 ppm is approximately equal to Therefore, the detection limit of 1.5 nM corresponds to approximately 0.037 ppm. In actual systems, considering temperature and pressure fluctuations as well as optical noise, the detection limit is conservatively calibrated to 0.1 ppm, which fully meets the early hydrogen permeation warning requirements for scenarios such as sulfur-containing natural gas pipelines.

[0161] Regarding the verification of signal-to-noise ratio improvement (time-resolved fluorescence technique):

[0162] Time-resolved fluorescence (TRPL) technology effectively suppresses short-lived background noise (such as scattered light and impurity fluorescence) and preserves long-lived quantum dot fluorescence signals through gated acquisition, thereby significantly improving the signal-to-noise ratio (SNR).

[0163] In continuous-wave (CW) mode, the signal-to-noise ratio is SNR. CW After adopting TRPL mode, pulse excitation and delayed acquisition are used, with the bandwidth only turned on during the quantum dot fluorescence decay period. Acquisition gating. Quantum dot fluorescence lifetime. Gating width Under these conditions, the short-lived background is almost completely eliminated, and only the long-lived fluorescence signal of the quantum dots is collected. Limited by photon shot noise, the signal-to-noise ratio improvement factor of the TRPL mode is proportional to the square root of the ratio of signal accumulation time to the effective bandwidth of the noise, as theoretically stated in the formula:

[0164]

[0165] Substitute parameters (Quantum dot lifetime) (Time gate width), i.e., the signal-to-noise ratio improvement factor is 4.47 (amplitude ratio). The signal-to-noise ratio improvement is expressed in decibels (dB), with a 20log value used for amplitude signal-to-noise ratio. 10 Computation is equivalent to signal-to-noise ratio improvement This improvement enables the sensor to distinguish minute fluorescence changes of less than 5%, providing crucial support for high signal-to-noise ratio detection of extremely low concentrations of hydrogen permeation.

[0166] Secondly, the present invention also provides an application of a sulfur-resistant hydrogen permeation sensor based on the quantum dot fluorescence effect, employing the sulfur-resistant hydrogen permeation sensor based on the quantum dot fluorescence effect as described in the first aspect above, including hydrogen monitoring in sulfur-containing natural gas pipelines, hydrogen energy storage tanks, chemical hydrogenation devices, and nuclear power pressure vessels.

[0167] To better understand this technical solution, the following embodiments are provided for further explanation:

[0168] Quantum dot surface modification technology of the quantum dot sensing module 1:

[0169] By using thiol ligands (such as HS-CH2COOH) to form Fe-S bonds with the ZnS shell, the H2S adsorption energy is increased from 0.8 eV to 2.3 eV, blocking the H2S attack pathway. It maintains fluorescence stability for >2000 hours in a 1000 ppm H2S environment, with a cross-sensitivity of <0.5%, making it suitable for high sulfur content environments (e.g., 22.15 g / m³).

[0170] The core-shell structure optimization design of the quantum dot sensing module 1 is as follows:

[0171] The combination of CdSe core (2.5nm) + ZnS shell (3-5nm) balances hydrogen permeability and mechanical strength, and extends the operating temperature range to -20~150℃.

[0172] The fluorescence quenching response mechanism of the fluorescence detection module 2:

[0173] Based on the modified Stern-Volmer equation: I0 / I = 1 + Ksv·[H]·exp(-Ea / kT)

[0174] The quenching constant Ksv reaches 10 6 M⁻¹, 100x increase in sensitivity

[0175] The detection limit is as low as 0.1 ppm (compared to 10 ppm for conventional technologies).

[0176] Response time <30 seconds (traditional technology requires 30 minutes)

[0177] Time-resolved fluorescence (TRPL)

[0178] Signal-to-noise ratio improved by 20dB

[0179] It can detect weak fluorescence changes of less than 5%.

[0180] The multi-parameter coupling compensation algorithm of the signal processing module 3:

[0181] Temperature compensation accuracy ±0.5% (traditional ±15%)

[0182] Pressure compensation accuracy ±0.3% (traditional ±8%)

[0183] Gaussian attenuation filtering eliminates mechanical vibration noise

[0184] The false alarm rate decreased from 23% to 0.7%.

[0185] The above-disclosed embodiments are merely preferred embodiments of a sulfur-resistant hydrogen permeation sensor based on quantum dot fluorescence effect and its application, and should not be construed as limiting the scope of this application. Those skilled in the art can understand that all or part of the processes for implementing the above embodiments, and equivalent variations made in accordance with the claims of this application, still fall within the scope of this application.

Claims

1. A sulfur-resistant hydrogen permeation sensor based on quantum dot fluorescence effect, characterized in that, It includes a quantum dot sensing module, a fluorescence detection module, and a signal processing module. The quantum dot sensing module forms Fe-S bonds with the ZnS shell through thiol ligands, blocking the H2S adsorption pathway. The fluorescence detection module detects fluorescence quenching signals based on a modified Stern-Volmer equation and integrates time-resolved fluorescence technology. The signal processing module integrates temperature and pressure compensation algorithms and a Gaussian filtering model to eliminate pipeline vibration noise.

2. The sulfur-resistant hydrogen permeation sensor based on quantum dot fluorescence effect as described in claim 1, characterized in that, The quantum dot sensing module incorporates a sulfur resistance stability quantification formula and a surface coverage calculation formula. Formula for quantifying sulfur resistance stability: H2S adsorption energy calculation: ； in: : adsorption energy of H2S molecule on quantum dot surface; : Total energy of the system after adsorption onto thiol-modified quantum dots; The individual energy of thiol-modified quantum dots; The energy of an isolated H2S molecule; Thiol modification The adsorption energy is significantly increased, effectively blocking the chemical adsorption of H2S; Surface coverage calculation formula: Langmuir adsorption model: ； in: : Coverage of H2S on quantum dot surface; Adsorption equilibrium constant; Partial pressure of H2S gas; At a total pressure of 101.325 kPa, the corresponding partial pressure for H2S concentration of 1000 ppm is: After thiol modification, the experimental fit Substituting into the calculation, we get This indicates that the surface coverage of H2S was effectively suppressed.

3. The sulfur-resistant hydrogen permeation sensor based on quantum dot fluorescence effect as described in claim 1, characterized in that: The fluorescence detection module incorporates the original Stern-Volmer equation and multi-physics field coupling correction. The original Stern-Volmer equation: ； in: Initial fluorescence intensity in a hydrogen-free environment; Fluorescence intensity after hydrogen permeation; Stern-Volmer quenching constant, characterizing the sensor's sensitivity to hydrogen; : Hydrogen concentration in the environment to be tested; Multiphysics Coupling Correction To eliminate the cross-effects of temperature, pressure, and vibration on the fluorescence signal, the quenching constant is modified to be a function of temperature T and pressure P: ； in: The absolute temperature of the sensor's operating environment, expressed in Kelvin (K). Total pressure of the sensor's operating environment, in kPa; The effective quenching constant after temperature and pressure compensation is defined by the following formula: ； in: The baseline quenching constant under standard conditions; Temperature compensation function, using the Arrhenius modified form; The pressure compensation function adopts a power-law model. The temperature compensation function Defined as: ； in: Activation energy of hydrogen permeation process ; Boltzmann constant ; Reference temperature: 298K; The pressure compensation function Defined as: ； in: Reference pressure: 101.325 kPa; The pressure index obtained through experimental fitting based on Henry's law is 0.

7. Furthermore, vibration interference filtering employs an independent Gaussian model for post-processing to eliminate the interference of pipeline vibration noise on fluorescence intensity, reducing the false alarm rate from the traditional 23% to 0.7%; its expression is: ； in: Fluorescence intensity after vibration compensation; Measured fluorescence intensity; Real-time vibration acceleration of the sensor's environment, in m / s². 2 ; Characteristic vibration threshold When the vibration acceleration equals this value, the fluorescence intensity correction factor is: ; Through the above compensation and filtering, the sensor can still accurately invert hydrogen concentration under complex working conditions such as temperature fluctuations, pressure changes and mechanical vibrations, reducing the false alarm rate from 23% of the traditional method to 0.7%.

4. Application of a sulfur-resistant hydrogen permeation sensor based on quantum dot fluorescence effect, employing the sulfur-resistant hydrogen permeation sensor based on quantum dot fluorescence effect as described in any one of claims 1-3, characterized in that, This includes monitoring of hydrogen in sulfur-containing natural gas pipelines, hydrogen storage tanks, chemical hydrogenation units, and nuclear power pressure vessels.

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