Gas Cell Research Articles

Measurements of the Limit of Detection for Electrochemical Gas Sensors

Abstract Electrochemical amperometric gas cells are becoming the sensor of choice when measuring polluting gases using low-cost air quality networks. A number of technical issues remain to be resolved to deliver fit-for-purpose monitoring systems: humidity corrections are needed but not well understood, interfering gases such as ozone can have variable cross-sensitivity and calibration intervals, and procedures are still being investigated. Another unanswered question is the limit of detection (LOD) for electrochemical gas sensors. Estimates range from hundreds of equivalent parts per billion (ppbv) to single-digit ppbv concentrations. We discuss the LOD for nitrogen dioxide (NO2), an important gas when monitoring air quality. Multiple NO2 sensor systems were tested in an environmental chamber to determine, among other parameters, the LOD for NO2 electrochemical gas sensors. Low-noise electronics and battery powering further reduced electronic noise, allowing the intrinsic LOD of the electrochemical cell to be determined. Noise, quantified as the standard deviation in zero air in a very stable temperature and relative humidity–controlled chamber was <500 pA, which translated into 1.6 ppbv, so the LOD, 3 × standard deviation, was 4.8 ppb. Interestingly, the LOD calculated with 300 ppbv NO2 test gas was the same (±0.1 ppbv). Further tests with a higher resolution analog-to-digital converter resulted in the same LOD, further leading to the conclusion that for the Alphasense NO2-A43F NO2 sensor, the limiting value for LOD is 4.8 ppbv.

The impact of different batter mixing atmospheres on the quality of reduced sucrose sponge and cream cakes

Cakes are chemically-leavened sugar-rich bakery products. Depending on the cake type, air is incorporated differently during mixing. Sponge cake batter is a gas bubble rich foam, while cream cake batter is an emulsion containing less gas cells. Given the consumer interest in reduced sucrose food systems, we here examined the potential of using altered mixing atmospheres [pure nitrogen (N2) or carbon dioxide (CO2)] to improve reduced sucrose cake quality. The use of poorly soluble N2 resulted in voluminous, stable batter. This was especially the case for foam-type sponge cake batters. During baking of sponge and cream cake batters, leavening was similar for batters prepared either under air or N2, resulting in similar cake qualities. Use of the highly soluble CO2 as mixing atmosphere negatively affected batter density, but positively leavening during baking due to temperature-induced release of previously solubilized CO2. In foam-type sponge cake making, the significant negative effect of CO2 on batter density was not overruled by the positive effect of CO2 release during leavening/baking. In contrast, the CO2 mixing atmosphere during batter-type cream cake making had only a limited negative effect on batter density while greatly affecting leavening, and resulting in high-quality, voluminous (reduced sucrose) cakes.

Isolated attosecond pulse generation in a semi-infinite gas cell driven by time-gated phase matching

Isolated attosecond pulse (IAP) generation usually involves the use of short-medium gas cells operated at high pressures. In contrast, long-medium schemes at low pressures are commonly perceived as inherently unsuitable for IAP generation due to the nonlinear phenomena that challenge favourable phase-matching conditions. Here we provide clear experimental evidence on the generation of isolated extreme-ultraviolet attosecond pulses in a semi-infinite gas cell, demonstrating the use of extended-medium geometries for effective production of IAPs. To gain a deeper understanding we develop a simulation method for high-order harmonic generation (HHG), which combines nonlinear propagation with macroscopic HHG solving the 3D time-dependent Schrödinger equation at the single-atom level. Our simulations reveal that the nonlinear spatio-temporal reshaping of the driving field, observed in the experiment as a bright plasma channel, acts as a self-regulating mechanism boosting the phase-matching conditions for the generation of IAPs.

Optimization for hydrogen gas quantitative measurement using tunable diode laser absorption spectroscopy

Gas sensors are vital for safety, quality control, and environmental preservation across diverse industries. Tunable diode laser absorption spectroscopy (TDLAS) is widely employed for gas analysis due to its high sensitivity and selectivity. However, quantifying low concentrations of hydrogen gas using TDLAS in the infrared region proves challenging due to its lower absorption compared to other gases in the NIR region. This study introduces an innovative method for precise hydrogen gas measurement through the analysis of absorption spectra at different pressures and the employment of a high-pressure gas cell. By applying these methodologies to a calibration-free technique, we can realize the optimal measurement conditions for increasing the gas detection limit and stabilizing the wavelength lock for the laser diode. As a result, a linear relationship between hydrogen gas concentration and sensor response is achieved in the wide detection range of 0.01% to 100%. Under the optimal measurement conditions, our TDLAS system’s stability is demonstrated with minimum detection limits of 0.2866% and 0.0055% at integration times of 1 s and 30 s, respectively.

Effect of exogenous protein substitution in glutinous rice cake: Batter rheology, structure, and retrogradation behavior

The investigation focused on the batter properties, baking performance, and retrogradation behavior of gluten-free sponge cakes after partial (15%, 30%, and 45%) substitution of glutinous rice flour with exogenous protein, including whey protein isolates (WPI), egg white protein (EWP), and soy protein isolate (SPI). The viscoelastic properties and apparent viscosity of batter positively correlated with substitution levels, with SPI superior to WPI and EWP. WPI could produce batter with smaller and more evenly distributed cells, contributing to an enhanced specific volume of the cake due to its stabilizing effect of gas cells to form viscoelastic films. The gelatinization of starch granules proved to be constrained by the incorporation of WPI and SPI, as evidenced by elevated gelatinization temperature and reduced enthalpy change values. The restriction could be attributed to the strengthened hydrogen bonding between the starch and protein, which subsequently alleviated the retrogradation and water redistribution of cake during storage. An unpleasant eggy or beany flavor of cake was generated at 45% substitutions of EWP and SPI. In comparison, 30% WPI contributed to an appealing aroma and mouthfeel, making it a nutritional supplement to enhance its protein content while maintaining its fine sensory attributes of gluten-free sponge cake.

Miniaturizing gas sensors combining mid-infrared interband cascade light emitting diodes with substrate-integrated hollow waveguides

In this study, we report a compact and versatile gas sensor system combining mid-infrared interband cascade light emitting diodes (MIR-ICLEDs) with substrate-integrated hollow waveguides (iHWGs) toward miniaturized gas sensors. Two readily exchangeable MIR-ICLEDs with center emission wavelengths of 3.4 µm (2941 cm−1) and 5.7 µm (1754 cm−1), respectively, were integrated into a modular sensor system using the iHWG simultaneously as a miniaturized gas cell. The performance of the sensor system for quantitative analysis was evaluated based on calibration functions established for four analytes (i.e., methane, isobutane, acetone, and acetaldehyde) within the respective spectral regions. The utility of such a sensor system as a non-dispersive infrared sensor was tested for various scenarios, including the application of spectral filters, the performance of the individual ICLEDs, and in the analysis of gas mixtures. Furthermore, we demonstrated that the modularity of the sensor design facilitates flexible adaptation to target gas species and available sample volumes, differentiating individual components within gas mixtures.

A hybrid learning approach to better classify exhaled breath's infrared spectra: A noninvasive optical diagnosis for socially significant diseases.

Early diagnosis is crucial for effective treatment of socially significant diseases, such as type 1 diabetes mellitus (T1DM), pneumonia, and asthma. This study employs a diagnostic method based on infrared laser spectroscopy of human exhaled breath. The experimental setup comprises a quantum cascade laser, which emits in a pulsed mode with a peak power of up to 150 mW in the spectral range of 5.3-12.8 μm (780-1890 cm-1), and a Herriott multipass gas cell with a specific optical path length of 76 m. Using this setup, spectra of exhaled breath in the mid-infrared range were obtained from 165 volunteers, including healthy individuals, patients with T1DM, asthma, and pneumonia. The study proposes a hybrid approach for classifying these spectra, utilizing a variational autoencoder for dimensionality reduction and a support vector machine method for classification. The results demonstrate that the proposed hybrid approach outperforms other machine learning method combinations.

In Situ Gas and Liquid Cell Imaging and Spectroscopy of Nanocatalysts

In Situ Gas and Liquid Cell Imaging and Spectroscopy of Nanocatalysts

New Generation Environmental In Situ TEM Holder for Gas Cell Research Across Multiple Platforms

New Generation Environmental In Situ TEM Holder for Gas Cell Research Across Multiple Platforms

VUV absorption spectra of water and nitrous oxide by a double-duty differentially pumped gas filter.

The differentially pumped rare-gas filter at the end of the VUV beamline of the Swiss Light Source has been adapted to house a windowless absorption cell for gases. Absorption spectra can be recorded from 7 eV to up to 21 eV photon energies routinely, as shown by a new water and nitrous oxide absorption spectrum. By and large, the spectra agree with previously published ones both in terms of resonance energies and absorption cross sections, but that of N2O exhibits a small shift in the {\tilde{\bf D}} band and tentative fine structures that have not yet been fully described. This setup will facilitate the measurement of absorption spectra in the VUV above the absorption edge of LiF and MgF2 windows. It will also allow us to carry out condensed-phase measurements on thin liquid sheets and solid films. Further development options are discussed, including the recording of temperature-dependent absorption spectra, a stationary gas cell for calibration measurements, and the improvement of the photon energy resolution.

Signal enhancement of the gas detection based on quartz-enhanced photothermal spectroscopy technology.

This paper presents an improved gas sensor based on the dual-excitation of quartz-enhanced photothermal spectroscopy (QEPTS) using a single quartz tuning fork (QTF) for signal detection. The silver coating on one side of the QTF was chemically etched to increase the laser power interacted with QTF for QEPTS signal excitation. By etching the silver coating on one side of QTF, the reflection structure between the silver coating of the other side of QTF and the external flat mirror was established. The device uses an absorption gas cell with an optical range length of 3 m, making the laser beam interact with the gas more completely and posing more gas concentration information. Acetylene was selected as the target gas to verify the performance of the sensor. The experimental results show that the signal amplitude with a flat mirror was 1.41 times that without a flat mirror, and 2.47 times that of traditional QEPTS sensor. The system has a minimum detection limit (MDL) of 1.10 ppmv, corresponding to a normalized noise equivalent absorption coefficient (NNEA) of 7.14 × 10-9 cm-1·W·Hz-1/2. Allan variance analysis results show that when the integration time is 700 s, the MDL of the system is 0.21 ppmv. The proposed gas sensor can play an important role on detecting trace gas in many fields.

Tuning the Size of TiO2-Supported Co Nanoparticle Fischer-Tropsch Catalysts Using Mn Additions.

Modifying traditional Co/TiO2-based Fischer-Tropsch (FT) catalysts with Mn promoters induces a selectivity shift from long-chain paraffins toward commercially desirable alcohols and olefins. In this work, we use in situ gas cell scanning transmission electron microscopy (STEM) with energy-dispersive X-ray spectroscopy (EDS) elemental mapping, and near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) to demonstrate how the elemental dispersion and chemical structure of the as-calcined materials evolve during the H2 activation heat treatment required for industrial CoMn/TiO2 FT catalysts. We find that Mn additions reduce both the mean Co particle diameter and the size distribution but that the Mn remains dispersed on the support after the activation step. Density functional theory calculations show that the slower surface diffusion of Mn is likely due to the lower number of energetically accessible sites for the Mn on the titania support and that favorable Co-Mn interactions likely cause greater dispersion and slower sintering of Co in the Mn-promoted catalyst. These mechanistic insights into how the introduction of Mn tunes the Co nanoparticle size can be applied to inform the design of future-supported nanoparticle catalysts for FT and other heterogeneous catalytic processes.

Alkali-Induced Protein Structural, Foaming, and Air-Water Interfacial Property Changes and Quantitative Proteomic Analysis of Buckwheat Sourdough Liquor.

In this study, the protein structural, foaming, and air-water interfacial properties in dough liquor (DL) ultracentrifugated from buckwheat sourdough with different concentrations of an alkali (1.0-2.5% of sodium bicarbonate) were investigated. Results showed that the alkali led to the cross-linking of protein disulfide bonds through the oxidation of free sulfhydryl groups in DL. The alterations in protein secondary and tertiary structures revealed that the alkali caused the proteins in DL to fold, decreased the hydrophobicity, and led to a less flexible but compact structure. The alkali accelerated the diffusion of proteins and decreased the surface tension of DL. In addition, the alkali notably improved the foam stability by up to 34.08% at 2.5% concentration, mainly by increasing the net charge, reducing the bubble size, and strengthening the viscoelasticity of interfacial protein films. Quantitative proteomic analysis showed that histones and puroindolines of wheat and 13S globulin of buckwheat were closely related to the changes in the alkali-induced foaming properties. This study sheds light on the mechanism of alkali-induced improvement in gas cell stabilization and the buckwheat sourdough steamed bread quality from the aspect of the liquid lamella.

In-cell multi-nucleon transfer reactions at the FRS Ion Catcher

An exploratory program to establish the multi-nucleon transfer (MNT) reaction as a new research direction at the FRS Ion Catcher (FRS-IC) has started at GSI. Its long term goal is the use of secondary exotic beams from the Super-FRS to drive MNT reactions. The near term goal is to perform proof-of-principle cross section and mass measurements with slowed-down 238U beams on targets inside the FRS-IC gas cell. The experimental efficiencies and expected rates are estimated using production cross sections from the Langevin MNT model followed by simulations of the full setup. The impact of the space charge effect inside the gas cell is evaluated in detail.

Observation of d(t,n)α Neutrons Following d(d,p)t Reactions in a Deuterium Gas Cell: An Attempt to Repeat Ruhlig’s 1938 Observation of Secondary Reactions

In order to benchmark methods used to calculate reaction-in-flight fusion reactions in inertial confinement fusion and address issues related to the first claimed observation of d(t,n)α reactions in 1938, secondary d(t,n)α reactions have been observed following d(d,p)t reactions in deuterium gas. A pulsed 200-nA, 2.2-MeV deuterium beam from the Triangle Universities Nuclear Laboratory FN tandem accelerator was injected into a cylindrical multiatmosphere deuterium gas target. The incident beam traversed along the target cylinder’s 3-cm symmetry axis after its passage through a Havar entrance foil. Two different Havar foil thicknesses were used to obtain 1.5- and 0.6-MeV deuteron beams entering the deuterium cell. The cylinder’s radius was 2 cm to allow for d(d,p)t tritons emitted perpendicular to the beam to range out in the deuterium gas. The neutron emission from the cell was observed via its time of flight to a liquid scintillator placed at various angles to the beam direction, at a distance of 243 cm. Pulse-shape-discrimination techniques were used to separate neutron and gamma-ray signals seen in the liquid scintillator. The observed probability of ~2 × 10–4 for inducing secondary d(t,n)α fusion in the gas cell per d(d,p)t reaction is consistent with theoretical expectations.

Multi-functional gas cell in the vacuum ultraviolet free-electron laser beamline.

A long gas cell, filled with noble gas, is typically positioned between the undulator and the first mirror in the free-electron laser (FEL) beamline to attenuate the laser power as required by the end-stations. In addition to attenuation, the gas cell also serves important functions in various applications, such as spectrometer calibration, resolving power evaluation during beamline commissioning, and filtering of third harmonic in FEL operations. These functions of the gas cell have been successfully tested and implemented at the Dalian Coherent Light Source, a vacuum ultraviolet FEL facility located in Dalian, China. The resolving power of higher than 5000 has been obtained, and accurate calibration has been completed using the gas cell. During operation, the third harmonic of the FEL was attenuated by approximately one order of magnitude with almost the same power of the fundamental. This greatly improved the signal-to-noise ratio at the end-stations.

Tunable optical parametric oscillator based on ZnGeP2 crystal for greenhouse gas remote sensing systems

This work is devoted to the development of a compact source of coherent radiation with frequency-energy characteristics and a spectral generation range that allows remote determination of background concentrations of greenhouse gases in the atmosphere. The aim of this work was to create a frequency parametric converter based on ZGP, pumped by Ho:YAG laser radiation. For use as a source in a mobile lidar for remote determination of the concentration of greenhouse gases in the atmosphere. In the course of the research, a layout of an Optical parametric oscillator OPO based on a ZGP crystal with Ho:YAG laser radiation pumping was developed. The system’s continuous failure-free operation time was 1.5 h at a pulse repetition rate of 10 kHz and a pulse energy of the generated radiation of 0.08 mJ. The tuning range of the OPO was from 3.3 to 5 μm when using a Lyot filter. The losses from the average generation power when the Lyot filter was introduced into the resonator were 30%. At the same time, it was possible to achieve a linewidth of the generated radiation of 0.7 nm. The divergence of the generated radiation did not exceed 1.5 mrad.The absorption spectrum of gases CO2, CH4, N2O, CO in a gas cell was simulated for the entire generation range of the ZnGeP2-based OPO. As a result of the simulation, the most intense absorption lines of gases CO2, CH4, N2O, CO in the OPO tuning range were revealed, the central wavelengths of the absorption lines and their spectral width were determined.

Methane sensing in the mid-IR using short wave IR photon counting detectors via non-linear interferometry

We demonstrate a novel MIR methane sensor shifting measurement wavelength to SWIR (1.55μm) by using non-linear interferometry. The technique exploits the interference effects seen in three-wave mixing when pump, signal, and idler modes make a double pass through a nonlinear crystal. The method allows sensing at wavelengths where detectors are poor (>3μm) and detection at wavelengths where photon counting sensitivity can be achieved. In a first experimental demonstration, we measured a small methane concentration inside a gas cell with high precision. This interferometer can be built in a compact design for field operations and potentially enable the detection of low concentrations of methane at up to 100m range. Signal-to-noise ratio calculations show that the method can outperform existing short wavelength (∼1.65μm) integrated path differential absorption direct sensing at high (>10−4) non-linear gain.

Performance of a High-Speed Pyroelectric Receiver as Cryogen-Free Detector for Terahertz Absorption Spectroscopy Measurements

The application of terahertz (THz) radiation in scientific research as well as in applied and commercial technology has expanded rapidly in recent years. One example is the progress in high-resolution THz spectroscopy based on quantum cascade lasers, which has enabled new observations in astronomy, atmospheric research, and plasma diagnostics. However, the lack of easy-to-use and miniaturised detectors has hampered the development of compact THz spectroscopy systems out of the laboratory environment. In this paper, we introduce a new high-speed pyroelectric receiver as a cryogen-free detector for THz absorption spectroscopy. Its performance is characterised by absorption spectroscopy measurements on a reference gas cell (RGC) with ammonia using a tunable THz quantum cascade laser at approximately 4.75 THz as the light source. It is shown that the receiver can record spectra up to 281 Hz without any artefacts to the observed spectral absorption profile, and the results reproduce the known pressure of ammonia in the RGC. This demonstrates that the pyroelectric receiver can be reliably used as an alternative to helium-cooled bolometers for absorption spectroscopy measurements in the THz range, with its main advantages being the high bandwidth, compactness, relatively low cost, and room-temperature operation. Its simplicity and high sensitivity make this receiver a key component for compact THz spectroscopy systems.

Fabry-Pérot photothermal interferometry in a hollow-core antiresonant fiber for gas detection in mid-infrared

Hollow-core antiresonant fiber can simultaneously act as a miniature gas cell and the light guidance with broad wavelength range, introducing an powerful tool to photothermal spectrosocpy and sensitive gas detection. Photothermal interferometry (PTI) is a spectroscopic tehcnique that employs an interferometer to finely measure the photothermal signal of trace gas. By splicing the HC-ARF between solid core fibers, a Fabry-Pérot (F-P) cavity is formed and enables PTI with a brief in-line design. However, the previous structure commonly adopted single-mode solid core fibers and might introduce large optical loss due to mode field mismatch, particularly for MIR pump laser. This could lead to significant decrease in sensitivity. Besides, the gas pressure effect on the HC-ARF-based PTI gas sensor had not been fully studied. In this work, we demonstrated the PTI for 13CO2 detection at 4.35 µm by employing an HC-ARF with a 100-µm core. An InF3 multimode fiber was utilized for the efficient delivery of MIR pump beam and successfully enhanced the pump power by a factor of 6.7. The limit of detection was determined to be 0.4 ppb at the integration time of 240 s. Finally, the relationship between gas pressure and photothermal signal was experimentally studied and compared with theoretical results.