Re-injection off-axis integrated cavity output spectroscopy for the simultaneous detection of N2O, H2O and CO with a mid-infrared QCL laser.

Off-axis integrated cavity output spectroscopy (OA-ICOS) has attracted much interest because it potentially allows highly sensitive field measurements with robust optical alignment. In this paper, a novel instrument that employs a high-finesse optical cavity as an absorption cell has been developed for sensitive measurements of multi-component gases N2O, H2O and CO in the atmosphere based on a mid-infrared quantum cascade laser (QCL) and OA-ICOS. In order to improve the energy utilization and increase the signal-to-noise ratio (SNR) of the signal, a new type of optical path structure of the laser re-injection method is adopted. Furthermore, the system performance can be effectively improved by using a new intervention method of injecting radio frequency (RF) white noise into a laser driver to suppress cavity mode noise and combining the wavelength modulation method (WMS). We compared the sensitivity of the second harmonic signal demodulation between the re-injection method and the standard OA-ICOS, and the SNR increased by 2.68 times compared to the latter. Analysis of the spectral measurements with Allan variance indicates that within an integration time of 1 s, the measurement accuracy of N2O, H2O, and CO is 6.71 ppb, 13.945 ppm, and 1.81 ppb, respectively, and within an integration time of 820 s, the measurement accuracy of N2O, H2O, and CO can be further improved to 1.26 ppb, 2.089 ppm, and 172 ppt, respectively. Our approach represents an underlying analytical method that provides guidelines for monitoring of representative gases in the atmosphere, industrial processes, emergency safety, etc.

Method of adaptive wide dynamic range gas concentration detection based on optimized direct absorption spectroscopy.

For wide dynamic range gas concentration detection based on tunable diode laser absorption spectroscopy (TDLAS), direct absorption spectroscopy (DAS) and wavelength modulation spectroscopy (WMS) are usually used in combination. However, in some application scenarios such as high-speed flow field detection, natural gas leakage, or industrial production, the requirements of wide-range, fast response and calibration-free must be met. Taking applicability and cost of TDALS-based sensor into consideration, a method of optimized direct absorption spectroscopy (ODAS) based on signal correlation and spectral reconstruction is developed in this paper. This method can achieve adaptive selection of the optimal benchmark spectrum for spectral reconstruction. Moreover, methane (CH4) is taken as an example to carry out the experimental verification. Experimental results proved that the method satisfies wide dynamic range detection of more than 4 orders of magnitude. It is worth noting that when measuring large absorbance with concentration of 75 × 104 ppm with DAS and ODAS method, respectively, the maximum value of residual is reduced from 3.43 to 0.07. Furthermore, whether measuring gas of small or large absorbance with different concentrations, which vary from 100 ppm to 75 × 104 ppm, the correlation coefficient between standard concentrations and inverted concentrations is 0.997, showing the linear consistency of the method in wide dynamic range. In addition, the absolute error is 1.81 × 104 ppm when measuring large absorbance of 75 × 104 ppm. It greatly improves the accuracy and reliability with the new method. In summary, the ODAS method can not only fulfill the measurement of gas concentration in wide range, but also further expand the application prospects of TDLAS.

Development of a Rapid Measurement Method for Analysis of the NOx Conversion Process Based on Quantum Cascade Laser Absorption Spectroscopy.

In this study, a method for double-beam quantum cascade laser absorption spectroscopy (DB-QCLAS) was developed. Two mid-infrared distributed feedback quantum cascade laser beams were coupled in an optical cavity for the monitoring of NO and NO2 (NO at 5.26 µm; NO2 at 6.13 µm). Appropriate lines in the absorption spectra were selected, and the influence of common gases in the atmosphere, such as H2O and CO2, was avoided. By analyzing the spectral lines under different pressure conditions, the appropriate measurement pressure of 111 mbar was selected. Under this pressure, the interference between adjacent spectral lines could be effectively distinguished. The experimental results show that the standard deviations for NO and NO2 were 1.57 ppm and 2.67 ppm, respectively. Moreover, in order to improve the feasibility of this technology for detecting chemical reactions between NO and O2, the standard gases of NO and O2 were used to fill the cavity. A chemical reaction instantaneously began, and the concentrations of the two gases were immediately changed. Through this experiment, we hope to develop new ideas for the accurate and rapid analysis of the process of NOx conversion and to lay a foundation for a deeper understanding of the chemical changes in atmospheric environments.

A dual-gas sensor for simultaneous detection of methane and acetylene based on time-sharing scanning assisted wavelength modulation spectroscopy.

Methane (CH4) and acetylene (C2H2) are important bioscience and chemical gases. The real-time monitoring and analysis of them have important research value in industrial process control. The time-sharing scanning assisted wavelength modulation spectroscopy (WMS) technique is developed for real-time and simultaneous detection of CH4 and C2H2. This system involves two near-infrared distributed feedback (DFB) lasers and a compact multipass cavity with an effective optical path of 52.2 m. The selected strong absorption lines of methane and acetylene are located at 6046.96 cm-1 and 6531.7 cm-1, respectively. The experiment environment is conducted at room temperature 23 °C and pressure 760 Torr. The sensor performance, including the minimum detection limit (MDL) and the stability, was improved by eliminating the influence of light intensity fluctuation using the WMS-2f/SAW technique. Allan deviation analysis indicates that a MDL of 0.1 ppm for CH4 and 0.2 ppm for C2H2 are achieved with 1-s integration time. And the instrument response time is about 44 s through the continuous analysis of standard gases. This sensitive, simple, reliable, and lowcost dual-gas sensor is very suitable for applications in the field environment, chemical process, and many other gas-phase analysis areas.

Development of a tunable diode laser absorption sensor for online monitoring of industrial gas total emissions based on optical scintillation cross-correlation technique.

We report the first application of gas total emission using a DFB diode laser for gas concentration measurements combined with two LEDs for gas velocity measurements. In situ gas total emissions and particle density measurements in an industrial pipeline using simultaneous tunable diode laser absorption spectroscopy (TDLAS) and optical scintillation cross-correlation technique (OSCC) are presented. Velocity mean values obtained are 7.59 m/s (OSCC, standard deviation is 1.37 m/s) and 8.20 m/s (Pitot tube, standard deviation is 1.47 m/s) in a steel plant pipeline for comparison. Our experiments demonstrate that the combined system of TDLAS and OSCC provides a new versatile tool for accurate measurements of total gas emissions.

Copper-catalyzed dimerization fragmentation cyclization reactions of (E)-1-en-4-yn-3-ols as a versatile approach for the synthesis of multisubstituted 1H-cyclopenta[b]naphthalenes.

An intermolecular condensation reaction of 1,3,5-triarylenynols catalyzed by copper is developed. This reaction is a straightforward method for the synthesis of highly conjugated 1H-cyclopenta[b]naphthalene. Fluorescent properties have been determined for some of the products.