Photoacoustic Heterodyne CO Sensor for Rapid Detection of CO Impurities in Hydrogen.

Hydrogen (H2) fuel cells have been developed as an environmentally benign, low-carbon, and efficient energy option in the current period of promoting low-carbon activities, which offer a compelling means to reduce carbon emissions. However, the presence of carbon monoxide (CO) impurities in H2 may potentially damage the fuel cell's anode. As a result, monitoring of the CO levels in fuel cells has become a significant area of research. In this paper, a novel photoacoustic sensor is developed based on photoacoustic heterodyne technology. The sensor combines a 4.61 µm mid-infrared quantum cascade laser with a low-noise differential photoacoustic cell. This combination enables fast, real-time online detection of CO impurity concentrations in H2. Notably, the sensor requires no wavelength locking to monitor CO online in real-time and produces a single effective signal with a period of only 15 ms. Furthermore, the sensor's performance was thoroughly evaluated in terms of detection sensitivity, linearity, and long-term stability. The minimum detection limit of 11 ppb was obtained at an optimal time constant of 1 s.

End-to-end methane gas detection algorithm based on transformer and multi-layer perceptron.

In this paper, an end-to-end methane gas detection algorithm based on transformer and multi-layer perceptron (MLP) for tunable diode laser absorption spectroscopy (TDLAS) is presented. It consists of a Transformer-based U-shaped Neural Network (TUNN) filtering algorithm and a concentration prediction network (CPN) based on MLP. This algorithm employs an end-to-end architectural design to extract information from noisy transmission spectra of methane and derive the CH4 concentrations from denoised spectra, without intermediate steps. The results demonstrate the superiority of the proposed TUNN filtering algorithm over other typically employed digital filters. For concentration prediction, the determination coefficient (R2) reached 99.7%. Even at low concentrations, R2 remained notably high, reaching up to 89%. The proposed algorithm results in a more efficient, convenient, and accurate spectral data processing for TDLAS-based gas sensors.

Noninvasive Skin Respiration (CO2) Measurement Based on Quartz-Enhanced Photoacoustic Spectroscopy.

A noninvasive method for disease diagnosis that does not require complex specialized laboratory facilities and chemical reagents is particularly attractive in the current medical environment. Here, we develop a noninvasive skin respiration sensor based on quartz-enhanced photoacoustic spectroscopy (QEPAS) that can monitor the skin elimination rate of carbon dioxide (CO2). A 3.8 mW distributed feedback laser emitting at 2.0 µm is used as an excitation source, and a three-dimensional (3D)-printed acoustic detection module is designed to apply to the skin as a sensor head. The performance of the noninvasive skin respiration sensor is assessed in terms of detection sensitivity, linearity, long-term stability, and water effect. A minimum detection limit of 35 ppb is achieved at the optimal integration time of 670 s. The skin respiration measurements from eight healthy volunteers are recorded, and the real-time results are analyzed.

Trace photoacoustic SO2 gas sensor in SF6 utilizing a 266†nm UV laser and an acousto-optic power stabilizer.

A sulfur dioxide (SO2) gas sensor based on the photoacoustic spectroscopy technology in a sulfur hexafluoride (SF6) gas matrix was demonstrated for SF6 decomposition components monitoring in the power system. A passive Q-switching laser diode (LD) pumped all-solid-state 266 nm deep-ultraviolet laser was exploited as the laser excitation source. The photoacoustic signal amplitude is linear related to the incident optical power, whereas, a random laser power jitter is inevitable since the immature laser manufacturing technology in UV spectral region. A compact laser power stabilization system was developed for better sensor performance by adopting a photodetector, a custom-made internal closed-loop feedback controller and a Bragg acousto-optic modulator (AOM). The out-power stability of 0.04% was achieved even though the original power stability was 0.41% for ∼ 2 hours. A differential two-resonator photoacoustic cell (PAC) was designed for weak photoacoustic signal detection. The special physical constants of SF6 buffer gas induced a high-Q factor of 85. A detection limit of 140 ppbv was obtained after the optimization, which corresponds to a normalized noise equivalent absorption coefficient of 3.2 × 10-9 cm-1WHz-1/2.

Clamp-type quartz tuning fork enhanced photoacoustic spectroscopy.

In this Letter, clamp-type quartz tuning fork enhanced photoacoustic spectroscopy (Clamp-type QEPAS) is proposed and realized through the design, realization, and testing of clamp-type quartz tuning forks (QTFs) for photoacoustic gas sensing. The clamp-type QTF provides a wavefront-shaped aperture with a diameter up to 1 mm, while keeping Q factors > 104. This novel, to the best of our knowledge, design results in a more than ten times increase in the area available for laser beam focusing for the QEPAS technique with respect to a standard QTF. The wavefront-shaped clamp-type prongs effectively improve the acoustic wave coupling efficiency. The possibility to implement a micro-resonator system for clamp-type QTF is also investigated. A signal-to-noise enhancement of ∼30 times has been obtained with a single-tube acoustic micro resonator length of 8 mm, ∼20% shorter than the dual-tube micro-resonator employed in a conventional QEPAS system.

Detection of Hydrogen Sulfide in Sewer Using an Erbium-Doped Fiber Amplified Diode Laser and a Gold-Plated Photoacoustic Cell.

A photoacoustic detection module based on a gold-plated photoacoustic cell was reported in this manuscript to measure hydrogen sulfide (H2S) gas in sewers. A 1582 nm distributed feedback (DFB) diode laser was employed as the excitation light source of the photoacoustic sensor. Operating pressure within the photoacoustic cell and laser modulation depth were optimized at room temperature, and the long-term stability of the photoacoustic sensor system was analyzed by an Allan-Werle deviation analysis. Experimental results showed that under atmospheric pressure and room temperature conditions, the photoacoustic detection module exhibits a sensitivity of 11.39 µV/ppm of H2S and can reach a minimum detection limit (1σ) of 140 ppb of H2S with an integration time of 1 s. The sensor was tested for in-field measurements by sampling gas in the sewer near the Shanxi University canteen: levels of H2S of 81.5 ppm were measured, below the 100 ppm limit reported by the Chinese sewer bidding document.

Palm-sized methane TDLAS sensor based on a mini-multi-pass cell and a quartz tuning fork as a thermal detector.

A palm-sized methane (CH4) tunable diode laser absorption spectroscopy (TDLAS) sensor is reported, in which a quartz tuning fork (QTF) is used as a thermal detector, working together with a mini-multi-pass cell (mini-MPC) to compose a gas detection module (GDM) with a compact dimension of 78 mm × 40 mm × 40 mm. A 1.65 µm near-infrared distributed feedback (DFB) laser is installed in the sensor for CH4 detection. A minimum detection limit (MDL) of 52 ppb is achieved at an integration time of 300 ms, corresponding to a normalized noise equivalent absorption coefficient (NNEA) of 2.1×10-8 cm-1W/Hz1/2. A seven-day continuous monitoring of atmospheric CH4 concentration is implemented to verify the sensor's long-term stability.

Three-Dimensional Printed Miniature Fiber-Coupled Multipass Cells with Dense Spot Patterns for ppb-Level Methane Detection Using a Near-IR Diode Laser.

Tunable diode laser absorption spectroscopy (TDLAS) based on a multipass cell (MPC) is a powerful analytical tool and is widely applied to air quality monitoring, industrial process control, and medical diagnostics. However, the conventional MPC as a core component in TDLAS devices has a large size, low utilization efficiency of the mirror surfaces, and tight optical alignment tolerances. In this paper, we design and fabricate a mini-MPC with an optical absorption path length of 4.2 m and dimensions of 4 × 4 × 6 cm3 (open cavity), which, to our best knowledge, is the current smallest MPC in terms of the same optical path length. The mini-MPC generates a seven-nonintersecting-circle dense spot pattern on two 25.4 mm spherical mirror surfaces, providing a high fill factor of 21 cm-2. A fiber-coupled collimator and an InGaAs photodetector are integrated into the mini-MPC via a high-resolution three-dimensional printed frame, hence removing the requirement of active optical alignment. Using a 1.65 µm distributed-feedback laser, the performance of this mini-MPC for methane detection was evaluated in terms of linearity, flow response time, stability, minimum detectable limit, and measurement precision. Continuous measurements of methane near a sewer and in the atmosphere were performed to demonstrate the stability and robustness of the highly integrated mini-MPC-based gas sensor. Our analysis shows that a methane minimum detectable limit of 117 ppbv is achieved, paving the way toward a sensitive, low-cost, and miniature trace gas sensor inherently suitable for large-scale deployment of distributed sensor networks and for handheld mobile devices.

Mid-Infrared Quartz-Enhanced Photoacoustic Sensor for ppb-Level CO Detection in a SF6 Gas Matrix Exploiting a T-Grooved Quartz Tuning Fork.

An optical sensor for highly sensitive detection of carbon monoxide (CO) in sulfur hexafluoride (SF6) was demonstrated by using the quartz-enhanced photoacoustic spectroscopy technique. A spectrophone composed of a custom 8 kHz T-shaped quartz tuning fork with grooved prongs and a pair of resonator tubes, to amplify the laser-induced acoustic waves, was designed aiming to maximize the CO photoacoustic response in SF6. A theoretical analysis and an experimental investigation of the influence of SF6 gas matrix on spectrophone resonance properties for CO detection have been provided, and the performances were compared with the standard air matrix. A mid-infrared quantum cascade laser with a central wavelength at 4.61 µm, resonant with the fundamental band of CO, and an optical power of 20 mW was employed as the light excitation source. A minimum detection limit of 10 ppb at 10 s of integration time was achieved, and a sensor response time of ∼3 min was measured.

Partial Least-Squares Regression as a Tool to Retrieve Gas Concentrations in Mixtures Detected Using Quartz-Enhanced Photoacoustic Spectroscopy.

We report on a statistical tool based on partial least-squares regression (PLSR) able to retrieve single-component concentrations in a multiple-gas mixture characterized by spectrally overlapping absorption features. Absorption spectra of mixtures of CO-N2O and mixtures of C2H2-CH4-N2O, both diluted in N2, were detected in the mid-IR range by exploiting quartz-enhanced photoacoustic spectroscopy (QEPAS) and using two quantum cascade lasers as light sources. Single-gas reference spectra of each target molecule were acquired and used as PLSR-based algorithm training data set. The concentration range explored in the analysis varies from a few parts-per-million (ppm) to thousands of ppm. Within this concentration range, the influence of the gas matrix on nonradiative relaxation processes can be neglected. Exploiting the ability of PLSR to deal with correlated data, these spectra were used to generate new simulated spectra, i.e., linear combinations of the reference ones. A Gaussian noise distribution was added to the created data set, simulating the real QEPAS signal fluctuations around the peak value. Compared with standard multilinear regression, PLSR predicted gas concentrations with a calibration error up to 5 times better, even with absorption features with spectral overlap greater than 97%.

Light-induced thermo-elastic effect in quartz tuning forks exploited as a photodetector in gas absorption spectroscopy.

We report on a study of light-induced thermo-elastic effects occurring in quartz tuning forks (QTFs) when exploited as near-infrared light detectors in a tunable diode laser absorption spectroscopy sensor setup. Our analysis showed that when the residual laser beam transmitted by the absorption cell is focused on the QTF surface area where the maximum strain field occurs, the QTF signal-to-noise ratio (SNR) is proportional to the strain itself and to the QTF accumulation time. The SNR was also evaluated when the pressure surrounding the QTF was lowered from 700 Torr to 5 Torr, resulting in an enhancement factor of ∽4 at the lowest pressure. At 5 torr, the QTF employed as light detector showed an SNR ∽6.5 times higher than that obtained by using a commercially available amplified photodetector.

Compact and Highly Sensitive NO2 Photoacoustic Sensor for Environmental Monitoring.

A nitrogen dioxide (NO2) photoacoustic sensor for environmental monitoring was developed using a low-cost high-power laser diode emitting at 450 nm. A compact low-noise photoacoustic detection module was designed to reduce the sensor size and to suppress noise. A LabVIEW-based control system was employed for the sensor. The parameters of the sensor were studied in detail in terms of laser power and operating pressure. The linearity of the sensor response with laser power and NO2 concentration confirms that saturation does not occur. At atmospheric pressure, a 3σ detection limit of 250 ppt (part per trillion by volume) was achieved with a 1-s averaging time, which corresponds to the specific detectivity of 3.173 × 10-9 W cm-1 Hz-1/2. A 72 h outdoor continuous on-line monitoring of environmental NO2 was implemented to demonstrate the reliability and validity of the developed NO2 sensor.

Ppb-Level Quartz-Enhanced Photoacoustic Detection of Carbon Monoxide Exploiting a Surface Grooved Tuning Fork.

A compact and sensitive carbon monoxide (CO) sensor was demonstrated by using quartz enhanced photoacoustic spectroscopy (QEPAS) exploiting a novel 15.2 kHz quartz tuning fork (QTF) with grooved surfaces. The custom QTF was designed to provide a quality factor as high as 15 000 at atmospheric pressure, which offers a high detection sensitivity. A large QTF prong spacing of 800 µm was selected, allowing one to avoid the use of any spatial filters when employing a quantum cascade laser as the excitation source. Four rectangular grooves were carved on two prong surfaces of the QTF to decrease the electrical resistance and hence enhance the signal amplitude. With water vapor as the catalyst for vibrational energy transfer, the sensor system using the novel surface grooved QTF achieved a CO minimum detection limit of 7 ppb for a 300 ms averaging time, which corresponds to a normalized noise equivalent absorption coefficient of 8.74 × 10-9 cm-1W /√Hz. Continuous measurements covering a seven-day period for atmospheric CO were implemented to verify the reliability and validity of the developed CO sensor system.

Dual-Gas Quartz-Enhanced Photoacoustic Sensor for Simultaneous Detection of Methane/Nitrous Oxide and Water Vapor.

The development of a dual-gas quartz-enhanced photoacoustic (QEPAS) sensor capable of simultaneous detection of water vapor and alternatively methane or nitrous oxide is reported. A diode laser and a quantum cascade laser (QCL) excited independently and simultaneously both the fundamental and the first overtone flexural mode of the quartz tuning fork (QTF), respectively. The diode laser targeted a water absorption line located at 7181.16 cm-1 (1.392 µm), while the QCL emission wavelength is centered at 7.71 µm and was tuned to target two strong absorption lines of methane and nitrous oxide, located at 1297.47 and 1297.05 cm-1, respectively. Two sets of microresonator tubes were positioned, respectively, at the antinode points of the fundamental and the first overtone flexural modes of the QTF to enhance the QEPAS signal-to-noise ratio. Detection limits of 18 ppb for methane, 5 ppb for nitrous oxide and 20 ppm for water vapor have been achieved at a lock-in integration time of 100 ms.

Piezo-enhanced acoustic detection module for mid-infrared trace gas sensing using a grooved quartz tuning fork.

A grooved quartz tuning fork (QTF) with a prong spacing of 800 µm for QEPAS application is reported. The prongs spacing is large enough to facilitate optical alignments when a degraded laser beam is used for QEPAS-based trace gas sensors. The grooved QTF has a resonance frequency of 15.2 kHz at atmospheric pressure and is characterized by four rectangular grooves carved on the QTF prong surfaces. With a grooved-prong, the electrical resistance R of the QTF is reduced resulting in an enhanced piezoelectric signal, while the Q factor is not affected, remaining as high as 15000 at atmospheric pressure. The geometric parameters of the acoustic micro resonators (AmRs) for on-beam QEPAS were optimized to match the grooved QTF, and a signal-to-noise gain factor of ∼ 30 was obtained with an optimum configuration. The performance of the QEPAS-based sensor was demonstrated exploiting an interband cascade laser (ICL) for CH4 detection and a 1σ normalized noise equivalent absorption (NNEA) coefficient of 4.1×10-9 cm-1 W/√Hz was obtained at atmospheric pressure.

Highly sensitive photoacoustic multicomponent gas sensor for SF6 decomposition online monitoring.

A ppb-level photoacoustic multicomponent gas sensor system for sulfur hexafluoride (SF6) decomposition detection was developed by the use of two near-infrared (NIR) diode lasers and an ultraviolet (UV) solid-state laser. A telecommunication fiber amplifier module was used to boost up the excitation optical power from the two NIR lasers. A dual-channel high-Q photoacoustic cell (PAC) was designed for the simultaneous detection of CO, H2S, and SO2 in SF6 buffer gas by means of a time division multiplexing (TDM) method. Feasibility and performance of the multicomponent sensor was evaluated, resulting in minimum detection limits of 435 ppbv, 89 ppbv, and 115 ppbv for CO, H2S, and SO2 detection at atmospheric pressure.

Quartz-enhanced photoacoustic sensor for ethylene detection implementing optimized custom tuning fork-based spectrophone.

The design and realization of two highly sensitive and easily interchangeable spectrophones based on custom quartz tuning forks, with a rectangular (S1) or T-shaped (S2) prongs geometry, is reported. The two spectrophones have been implemented in a QEPAS sensor for ethylene detection, employing a DFB-QCL emitting at 10.337 µm with an optical power of 74.2 mW. A comparison between their performances showed a signal-to-noise ratio 3.4 times higher when implementing the S2 spectrophone. For the S2-based sensor, a linear dependence of the QEPAS signal on ethylene concentration was demonstrated in the 5 ppm -100 ppm range. For a 10 s lock-in integration time, an ethylene minimum detection limit of 10 ppb was calculated.

Calculation model of dense spot pattern multi-pass cells based on a spherical mirror aberration.

We report a novel calculation model for dense spot pattern multi-pass cells consisting of two common identical spherical mirrors. A modified ABCD matrix without the paraxial approximation was developed to describe the ray propagation between two spherical mirrors and the reflection on the mirror surfaces. The intrinsic aberration from the spherical curvature creates a set of intricate variants with respect to a standard Herriot circle spot pattern. A series of detailed numerical simulations are implemented to verify that the input and output beams remain the same and, hence, retrace the same ray pattern. The set of exotic spot patterns obtained with a high fill factor improves the utilization efficiency of the mirror surfaces and produces a longer total optical path length with a low mirror cost.

Acoustic Detection Module Design of a Quartz-Enhanced Photoacoustic Sensor.

This review aims to discuss the latest advancements of an acoustic detection module (ADM) based on quartz-enhanced photoacoustic spectroscopy (QEPAS). Starting from guidelines for the design of an ADM, the ADM design philosophy is described. This is followed by a review of the earliest standard quartz tuning fork (QTF)-based ADM for laboratory applications. Subsequently, the design of industrial fiber-coupled and free-space ADMs based on a standard QTF for near-infrared and mid-infrared laser sources respectively are described. Furthermore, an overview of the latest development of a QEPAS ADM employing a custom QTF is reported. Numerous application examples of four QEPAS ADMs are described in order to demonstrate their reliability and robustness.

Acoustic Coupling between Resonator Tubes in Quartz-Enhanced Photoacoustic Spectrophones Employing a Large Prong Spacing Tuning Fork.

A theoretical model describing the acoustic coupling between two resonator tubes in spectrophones exploiting custom-made quartz tuning forks (QTFs) is proposed. The model is based on an open-end correction to predict the optimal tube length. A calculation of the sound field distribution from one tube exit allowed for the estimation of the optimal radius as a function of the QTF prong spacing and the sound wavelength. The theoretical predictions have been confirmed using experimental studies employing a custom QTF with a fundamental flexural mode resonance frequency of 15.8 kHz and a quality factor of 15,000 at atmospheric pressure. The spacing between the two prongs was 1.5 mm. Spectrophones mounting this QTF were implemented for the quartz-enhanced photoacoustic detection of water vapor in air in the mid-infrared spectral range.