Detection of C2H2 and HCl using mid-infrared degenerate four-wave mixing with stable beam alignment: towards practical in situ sensing of trace molecular species

A stable and convenient optical system to realize the forward phase-matching geometry for degenerate four-wave mixing (DFWM) is demonstrated in the mid-infrared spectral region by measuring DFWM signals generated in acetylene (C₂H₂) and hydrogen chloride (HCl) molecules by probing the fundamental ro-vibrational transitions. IR laser pulses tunable from 2900 cm^?1 to 3350 cm^?1 with a 0.025 cm^?1 linewidth were obtained using a laser system composed of an injection seeded Nd:YAG laser, a dye laser, and a frequency mixing unit. At room temperature and atmospheric pressure, a detection limit of 35 ppm (～ 9.5×10¹⁴ molecules/cm³) for C₂H₂ was achieved in a gas flow of a C₂H₂/N₂ mixture by scanning the P(11) line of the (010(11)⁰)–(0000⁰0⁰) band. The detection limit of the HCl molecule was measured to be 25 ppm (～6.8×10¹⁴ molecules/cm³) in the same environment by probing the R(4) line. The dependences of signal intensities on molecular concentrations and laser pulse energies were demonstrated using C₂H₂ as the target species. The variations of the signal line shapes with changes in the buffer gas pressures and laser intensities were recorded and analyzed. The experimental setup demonstrated in this work facilitates the practical implementation of in situ, sensitive molecular species sensing with species-specific, spatial and temporal resolution in the spectral region of 2.7–3.3 μm (3000–3700 in cm^?1), where various molecular species important in combustion have absorption bands.     

Template-free hydrothermal synthesis of ZnO microrods for gas sensor application

Zinc oxide microrods with controlled diameter were prepared without the addition of template and additive by a simple hydrothermal route only using Zn(CH₃COO)₂·2H₂O as a precursor. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and electron diffraction (ED). The crystal structure of prepared ZnO microrods is hexagonal phase polycrystalline with zincite structure. With the increase of the precursor concentration from 0.05 M to 0.6 M, the diameter of the ZnO microrods increased from 1 μm to 5 μm. A localized oriented attachment mechanism was prepared to account for the formation of ZnO microrods. The gas-sensing performance experiments indicated that the prepared ZnO microrods exhibited highly sensitive, selective gas-sensing properties, and good stability to acetone vapor. The response and recovery time of ZnO-based gas sensor to 100 ppm acetone vapor are 12 s and 18 s, respectively. The mechanism of the ZnO-based sensor was investigated.     

Scanned-wavelength-modulation spectroscopy near 2.5 μm for H2O and temperature in a hydrocarbon-fueled scramjet combustor

The design and demonstration of a two-color tunable diode laser sensor for measurements of temperature and H₂O in an ethylene-fueled model scramjet combustor are presented. This sensor probes multiple H₂O transitions in the fundamental vibration bands near 2.5 μm that are up to 20 times stronger than those used by previous near-infrared H₂O sensors. In addition, two design measures enabled high-fidelity measurements in the nonuniform flow field. (1) A recently developed calibration-free scanned-wavelength-modulation spectroscopy spectral-fitting strategy was used to infer the integrated absorbance of each transition without a priori knowledge of the absorption lineshape and (2) transitions with strengths that scale near-linearly with temperature were used to accurately determine the H₂O column density and the H₂O-weighted path-averaged temperature from the integrated absorbance of two transitions.     

Synthesis of Au-functionalized SnO2 nanotubes using TeO2 nanowires as templates and their enhanced gas sensing properties

Au-functionalized SnO₂ nanotubes were prepared for use as gas sensors using TeO₂ nanowires as templates. Transmission electron microscopy revealed tube diameters, tube lengths and tube wall thicknesses ranging from 50 to 200 nm, 5 to 50 μm, and 13 to 18 nm, respectively. The Au-functionalized SnO₂ nanotube sensors showed responses of 179–473 % to 1–5 ppm NO₂ at 300 ^°C. These values are much higher than those obtained using bare SnO₂ nanotubes synthesized in this study and most other SnO₂ one-dimensional nanostructure-based sensors reported in the literature. The NO₂ gas sensing mechanism of the Au-functionalized SnO₂ nanotube sensors is also discussed.     

Enhanced ethanol sensing properties of TiO2/ZnO core–shell nanorod sensors

TiO₂-core/ZnO-shell nanorods were synthesized using a two-step process: the synthesis of TiO₂ nanorods using a hydrothermal method followed by atomic layer deposition of ZnO. The mean diameter and length of the nanorods were ～300 nm and ～2.3 μm, respectively. The cores and shells of the nanorods were monoclinic-structured single-crystal TiO₂ and wurtzite-structured single-crystal ZnO, respectively. The multiple networked TiO₂-core/ZnO-shell nanorod sensors showed responses of 132–1054 % at ethanol (C₂H₅OH) concentrations ranging from 5 to 25 ppm at 150 ^°C. These responses were 1–5 times higher than those of the pristine TiO₂ nanorod sensors at the same C₂H₅OH concentration range. The substantial improvement in the response of the pristine TiO₂ nanorods to C₂H₅OH gas by their encapsulation with ZnO may be attributed to the enhanced absorption and dehydrogenation of ethanol. In addition, the enhanced sensor response of the core–shell nanorods can be attributed partly to changes in resistance due to both the surface depletion layer of each core–shell nanorod and the potential barriers built in the junctions caused by a combination of homointerfaces and heterointerfaces.     

T-shape microresonator-based quartz-enhanced photoacoustic spectroscopy for ambient methane monitoring using 3.38-μm antimonide-distributed feedback laser diode

This paper reports on the development of a gas sensor involving a newly available 3.38-μm distributed feedback laser in combination with a novel T-shape microresonator-based quartz-enhanced photoacoustic spectroscopy (T-mR QEPAS), capable of simultaneous monitoring of multi-species (such as CH₄, H₂CO, HCl, C₂H₄) using the same QEPAS spectrophone. As a first demonstration, monitoring of ambient methane (CH₄) was achieved at atmospheric pressure with a 1σ detection limit of 400 ppbv (parts per billion by volume) in an integration time of 10 s and a water vapor concentration of 1.15 vol% (11,500 ppm) in the atmosphere, which is very suitable for field measurement of CH₄ emission.     

Multi-species laser absorption sensors for in situ monitoring of syngas composition

Tunable diode laser absorption spectroscopy sensors for detection of CO, CO₂, CH₄ and H₂O at elevated pressures in mixtures of synthesis gas (syngas: products of coal and/or biomass gasification) were developed and tested. Wavelength modulation spectroscopy (WMS) with 1f-normalized 2f detection was employed. Fiber-coupled DFB diode lasers operating at 2325, 2017, 2290 and 1352 nm were used for simultaneously measuring CO, CO₂, CH₄ and H₂O, respectively. Criteria for the selection of transitions were developed, and transitions were selected to optimize the signal and minimize interference from other species. For quantitative WMS measurements, the collision-broadening coefficients of the selected transitions were determined for collisions with possible syngas components, namely CO, CO₂, CH₄, H₂O, N₂ and H₂. Sample measurements were performed for each species in gas cells at a temperature of 25 °C up to pressures of 20 atm. To validate the sensor performance, the composition of synthetic syngas was determined by the absorption sensor and compared with the known values. A method of estimating the lower heating value and Wobbe index of the syngas mixture from these measurements was also demonstrated.     

UV-enhanced room-temperature gas sensing of ZnGa2O4 nanowires functionalized with Au catalyst nanoparticles

ZnGa₂O₄ nanowires were synthesized using a thermal evaporation technique. Scanning electron microscopy, transmission electron microscopy, and X-ray diffraction revealed that the nanowires were single crystals 30–200 nm in diameter and ranged up to ～100 μm in length. The sensing properties of multiple networked ZnGa₂O₄ nanowire sensors functionalized with Au catalyst nanoparticles with diameters of a few nanometers toward NO₂ gas at room temperature under UV irradiation were examined. The sensors showed a remarkably enhanced response and far reduced response and recovery times toward NO₂ gas at room temperature under 254 nm-ultraviolet (UV) illumination. The response of ZnGa₂O₄ nanowires to NO₂ gas at room temperature increased from ～100 to ～861 % with increasing the UV intensity from 0 to 1.2 mW/cm². The significant improvement in the response of ZnGa₂O₄ nanowires to NO₂ gas by UV irradiation is attributed to the increased change in resistance due to the increase in the number of electrons participating in the reactions with NO₂ molecules by photo-generation of electron–hole pairs.     

Thermal stability and photoluminescence property of hexagonal MoO3·0.55H2O microrods

The metastable phase of well-faceted, hexagonal, prism-like molybdenum oxide hydrate (MoO₃·0.55H₂O) was successfully synthesized by evaporating molybdic acid solution prepared through cation membrane electrolysis of Na₂MoO₄·2H₂O aqueous solution. The obtained crystals were characterized by X-ray diffraction (XRD), thermogravimetric (TG), scanning electronic microscopy (SEM) and photoluminescence (PL) spectrophotometry. The as-prepared MoO₃·0.55H₂O rods were of 2–4 μm in width and 5–12 μm in length. The MoO₃·0.55H₂O microrods displayed photoluminescence properties at room temperature and were transformed into stable orthorhombic α-MoO₃ after air annealing at 380 °C. Moreover, the influence of temperature factor on the phase transformation process, morphology and photoluminescence properties of MoO₃·0.55H₂O was investigated in detail.     

Fabrication of gas ionization sensor based on titanium oxide nanotube arrays

Gas sensors have been fabricated based on field ionization from titanium oxide nanotubes grown on titanium foil. Ordered nanaotube arrays of titanium oxides were grown by the anodization method. We measured breakdown voltages and discharge currents of the device for various gases. Our gas ionization sensors (GIS) presented good sensitivity, selectivity, and short response time. The GISs based on TiO₂ nanotube arrays showed lower breakdown voltage, higher discharge current, and good selectivity. An excellent response observed for Ar compared to other gases. Besides, by introducing 2 % CO and 4 % H₂ to N₂ flow gas, the amount of breakdown voltage shifts about 20 and 70 volts to the lower values, respectively. The GIS works at room temperature and has the ability of detect inert gases with high stability and good linearity. Besides, short response time of about 1 second for the GISs based on TiO₂ nanotube arrays makes them excellent for gas sensing applications. Sharp edges of the nanotubes, through enhancing the applied electric field, reduce operating voltage to the reasonable values and power consumption.     

A mid-infrared scanned-wavelength laser absorption sensor for carbon monoxide and temperature measurements from 900 to 4000 K

Mid-infrared laser absorption sensors based on quantum cascade laser (QCL) technology offer the potential for high-sensitivity, selective, and high-speed measurements of temperature and concentration for species of interest in high-temperature environments, such as those found in combustion devices. A new mid-infrared QCL absorption sensor for carbon monoxide and temperature measurements has been developed near the intensity peak of the CO fundamental band at 4.6 μm, providing orders-of-magnitude greater sensitivity than the overtone bands accessible with telecommunications lasers. The sensor is capable of probing the R(9), R(10), R(17), and R(18) transitions of the CO fundamental ro-vibrational band which are located at frequencies where H₂O and CO₂ spectral interference is minimal. Temperature measurements are made via scanned-wavelength two-line ratio techniques using either the R(9) and R(17) or the R(10) and R(18) line pairs. The high-speed (1–2 kHz) scanned-wavelength sensor is demonstrated in room-temperature gas cell measurements of CO and, to demonstrate the potential of the sensor for high-temperature thermometry, in shock-heated gases containing CO for a very wide range of temperature (950–3500 K) near 1 atm. To our knowledge, these measurements represent the first use of QCL-based absorption sensor for thermometry at elevated combustion-like temperatures. The high-temperature measurements of CO mole fraction and temperature agree with the post-reflected-shock conditions within ±1.5% and ±1.2% (1σ deviation), respectively.     

CW DFB RT diode laser-based sensor for trace-gas detection of ethane using a novel compact multipass gas absorption cell

The development of a continuous wave, thermoelectrically cooled (TEC), distributed feedback diode laser-based spectroscopic trace-gas sensor for ultra-sensitive and selective ethane (C₂H₆) concentration measurements is reported. The sensor platform used tunable diode laser absorption spectroscopy (TDLAS) and wavelength modulation spectroscopy as the detection technique. TDLAS was performed using an ultra-compact 57.6 m effective optical path length innovative spherical multipass cell capable of 459 passes between two mirrors separated by 12.5 cm and optimized for the 2.5–4 μm range TEC mercury–cadmium–telluride detector. For an interference-free C₂H₆ absorption line located at 2,976.8 cm^?1, a 1σ minimum detection limit of 740 pptv with a 1 s lock-in amplifier time constant was achieved.     

Sensitive detection of CO2 concentration and temperature for hot gases using quantum-cascade laser absorption spectroscopy near 4.2 μm

Mid-infrared quantum-cascade laser (QCL) absorption spectroscopy of CO₂ near 4.2 μm has been developed for measurement of temperature and concentration in hot gases. With stronger absorption line-strengths than transitions near 1.5, 2.0, and 2.7 μm used previously, the fundamental band (00⁰1–00⁰0) of CO₂ near 4.2 μm provides greatly enhanced sensitivity and accuracy to sense CO₂ in high-temperature gases. Line R(74) and line R(96) are chosen as optimum pair for sensitive temperature measurements due to their high-temperature sensitivity, equal signal-to-noise ratio (SNR), weak interference of H₂O transitions, as well as relatively strong line-strengths in high temperature and weak absorption in room temperature. The high-resolution absorption spectrum of the far wings of the R-branch (R56–R100) in the fundamental vibrational band of CO₂ is measured in a heated cell over the range 2,384–2,396 cm^?1 at different temperatures from 700 to 1,200 K. Taking three factors into consideration, including SNR, concentration detectability, and uncertainty sensitivity, the absorption line R(74) is selected to calculate CO₂ concentration. The tunable QCL absorption sensor is validated in mixtures of CO₂ and N₂ in a static cell for temperature range of 700–1,200 K, achieving an accuracy of ±6 K for temperature and ±5 % for concentration measurements.     

In situ sensor for cycle-resolved measurement of temperature and mole fractions in IC engine exhaust gases

We present a multi-species mole fraction and temperature sensor for in situ exhaust gas diagnostic of internal combustion (IC) engines. The sensor is based on Tunable Diode Laser Absorption Spectroscopy (TDLAS) and incorporates four optical channels - two miniature White cells and two double-traversal cells - with base lengths of 6?cm. It has been demonstrated at a hot air test stand and in the exhaust manifold of a single-cylinder research engine, with measured temperatures of up to 1000?K. Stable operation was achieved with absorption lengths of up to 192?cm (test stand) and 97?cm (engine). Employing time-division multiplexed detection, six species were measured simultaneously in the engine exhaust, at wavelengths ranging from 1.4?µm to 5.2 µm: water vapor (H₂O), carbon dioxide (CO₂), carbon monoxide (CO), methane (CH₄), nitrogen dioxide (NO₂) and nitric oxide (NO). The effective measurement rate was as high as 1?kHz, and cycle-to-cycle variations were clearly detected. We show the correlation of the air-fuel equivalence ratio with the spectroscopically measured mole fraction of each species. At a cycle-resolved rate, detection limits for the legally regulated species NO and NO₂ were 1?ppm and 4?ppm, respectively. The sensor is intended to help improve the understanding of IC engine emission behavior during fast transients.     

Quartz-enhanced photoacoustic spectroscopy-based sensor system for sulfur dioxide detection using a CW DFB-QCL

Sulfur dioxide (SO₂) trace gas detection based on quartz-enhanced photoacoustic spectroscopy (QEPAS) using a continuous wave, distributed feedback quantum cascade laser operating at 7.24 μm was performed. Influence of water vapor addition on monitored QEPAS SO₂ signal was also investigated. A normalized noise equivalent absorption coefficient of NNEA (1σ) = 1.21 × 10^?8 cm^?1 W Hz^?1/2 was obtained for the ν ₃ SO₂ line centered at 1,380.93 cm^?1 when the gas sample was moisturized with 2.3 % H₂O. This corresponds to a minimum detection limit (1σ) of 63 parts per billion by volume for a 1 s lock-in time constant.     

Dependence of the selectivity of SnO2 nanorod gas sensors on functionalization materials

Effects of functionalization materials on the selectivity of SnO₂ nanorod gas sensors were examined by comparing the responses of SnO₂ one-dimensional nanostructures functionalized with CuO and Pd to ethanol and H₂S gases. The response of pristine SnO₂ nanorods to 500 ppm ethanol was similar to 100 ppm H₂S. CuO-functionalized SnO₂ nanorods showed a slightly stronger response to 100 ppm H₂S than to 500 ppm ethanol. In contrast, Pd-functionalized SnO₂ nanorods showed a considerably stronger response to 500 ppm ethanol than to 100 ppm H₂S. In other words, the H₂S selectivity of SnO₂ nanorods over ethanol is enhanced by functionalization with CuO, whereas the ethanol selectivity of SnO₂ nanorods over H₂S is enhanced by functionalization with Pd. This result shows that the selectivity of SnO₂ nanorods depends strongly on the functionalization material. The ethanol and H₂S gas sensing mechanisms of CuO- and Pd-functionalized SnO₂ nanorods are also discussed.     

In situ TDLAS measurement of absolute acetylene concentration profiles in a non-premixed laminar counter-flow flame

Acetylene (C₂H₂), as an important precursor for chemiluminescence species, is a key to understand, simulate and model the chemiluminescence and the related reaction paths. Hence we developed a high resolution spectrometer based on direct Tunable Diode Laser Absorption Spectroscopy (TDLAS) allowing the first quantitative, calibration-free and spatially resolved in situ C₂H₂ measurement in an atmospheric non-premixed counter-flow flame supported on a Tsuji burner. A fiber-coupled distributed feedback diode laser near 1535 nm was used to measure several absolute C₂H₂ concentration profiles (peak concentrations up to 9700 ppm) in a laminar non-premixed CH₄/air flame (T up to 1950 K) supported on a modified Tsuji counter-flow burner with N₂ purge slots to minimize end flames. We achieve a fractional optical resolution of up to 5×10^?5 OD (1σ) in the flame, resulting in temperature-dependent acetylene detection limits for the P17e line at 6513 cm^?1 of up to 2.1 ppm?m. Absolute C₂H₂ concentration profiles were obtained by translating the burner through the laser beam using a DC motor with 100 μm step widths. Intercomparisons of the experimental C₂H₂ profiles with simulations using our new hydrocarbon oxidation mechanisms show excellent agreement in position, shape and in the absolute C₂H₂ values.     

Surface characterization and H2S-sensing potential of iron molybdate particles produced by supercritical solvothermal method and subsequent oxidation

The mostly crystalline polymorph β-FeMoO₄ was prepared by solvothermal synthesis from organic precursors, followed by high temperature supercritical drying in an autoclave. Crystallization of the synthesized particles occurred during subsequent heat treatment at 350 °C, confirmed by X-ray diffraction pattern analysis. The presence of Fe³⁺ ions in the powder, both well-crystallized and amorphous after heat treatment at 500 °C, was confirmed by room temperature Mössbauer spectrum. Thick-film gas sensors were prepared by conventional hand coating of a paste, the Fe₂(MoO₄)₃ powder mixed with an α-terpineol-based solvent, over the Au electrodes. The response of the prepared sensors to H₂S gas in the low concentration range 1–10 ppm in air was investigated. Moderately fast response and recovery times were observed. The iron molybdate, produced at low temperature, may be successfully used in the preparation of a H₂S gas sensor.     

Measurements of CO2 in a multipass cell and in a hollow-core photonic bandgap fiber at 2 μm

Recently, hollow-core photonic bandgap fibers (HC-PBFs) for use in the 2 μm wavelength region have become available. We have employed tunable diode laser absorption spectroscopy (TDLAS) to quantify CO₂ in nitrogen, injected into a HC-PBF. Our spectrometer contains both an HC-PBF-based absorption cell and an astigmatic Herriott multipass gas cell. The Herriott cell was used for comparison with the HC-PBF cell. The HC-PBF cell’s sensitivity and limit of detection were calculated to be 3.5×10^?4 cm^?1?Hz^?1/2 and 59 ppm?m, respectively. To substantiate the spectrometer performance, a measurement was done in the Herriott cell probing a reference gas mixture with nominal 400 μmol/mol CO₂ in N₂. The spectrometric results were in good agreement with the reference value. The relative standard uncertainty of the spectrometric result was found to be at the ±2 % level.     

NO Fluorescence Sensing by Europium Tetracyclines Complexes in the Presence of H2O2

The effect on the fluorescence of the europium:tetracycline (Eu:Tc), europium:oxytetracycline (Eu:OxyTc) and europium:chlortetracycline (Eu:ClTc) complexes in approximately 2:1 ratio of nitric oxide (NO), peroxynitrite (ONOO^?), hydrogen peroxide (H₂O₂) and superoxide (O₂ ^·?) was assessed at three ROS/RNS concentrations levels, 30 °C and pH 6.00, 7.00 and 8.00. Except for the NO, an enhancement of fluorescence intensity was observed at pH 7.00 for all the europium tetracyclines complexes—the high enhancement was observed for H₂O₂. The quenching of the fluorescence of the Tc complexes, without and with the presence of other ROS/RNS species, provoked by NO constituted the bases for an analytical strategy for NO detection. The quantification capability was evaluated in a NO donor and in a standard solution. Good quantification results were obtained with the Eu:Tc (3:1) and Eu:OxyTc (4:1) complexes in the presence of H₂O₂ 200 μM with a detection limit of about 3 μM (Eu:OxyTc).