MOF/Polymer-Integrated Multi-Hotspot Mid-Infrared Nanoantennas for Sensitive Detection of CO_(2) Gas

Metal-organic frameworks(MOFs)have been extensively used for gas sorption,storage and separation owing to ultrahigh porosity,exceptional thermal stability,and wide structural diversity.However,when it comes to ultra-low concentration gas detection,technical bottlenecks of MOFs appear due to the poor adsorption capacity at ppm-/ppblevel concentration and the limited sensitivity for signal transduction.Here,we present hybrid MOF-polymer physi-chemisorption mechanisms integrated with infrared(IR)nanoantennas for highly selective and ultrasensitive CO_(2) detection.To improve the adsorption capacity for trace amounts of gas molecules,MOFs are decorated with amino groups to introduce the chemisorption while maintaining the structural integrity for physisorption.Additionally,leveraging all major optimization methods,a multi-hotspot strategy is proposed to improve the sensitivity of nanoantennas by enhancing the near field and engineering the radiative and absorptive loss.As a benefit,we demonstrate the competitive advantages of our strategy against the state-of-the-art miniaturized IR CO_(2) sensors,including low detection limit,high sensitivity(0.18%/ppm),excellent reversibility(variation within 2%),and high selectivity(against C_(2)H_(5)OH,CH_(3)OH,N_(2)).This work provides valuable insights into the integration of advanced porous materials and nanophotonic devices,which can be further adopted in ultra-low concentration gas monitoring in industry and environmental applications.

Development of a Broadly Tunable Mid-Infrared Laser Source for Highly Sensitive Multiple Trace Gas Detection

A room-temperature broadly tunable mid-infrared difference frequency laser source for highly sensitive trace gas detection has been developed recently in our laboratory. The mid-infrared laser system is based on quasi-phase-matched （QPM） difference frequency generation （DFG） in a multigrating, temperature-controlled periodically poled LiNbO3 （PPLN） crystal and employs two near-infrared diode lasers as pump sources. The mid-infrared coherent radiation generated is tunable from 3.2 μm to 3.7μm with an output power of about 100 μW. By changing one of the pump laser head with another wavelength range, we can readily obtain other needed mid-infrared wavelength range cover. The performance of the mid-infrared laser system and its application to highly sensitive spectroscopic detection of CH4, HCl, CH2O, and NO2 has been carried out. A multi-reflection White cell was used in the experiment gaining ppb-level sensitivity. The DFG laser system has the features of compact, room-temperature operation, narrow line-width, and broadly continuous tunable range for potential applications in industry and environmental monitoring.

Up-conversion detection of mid-infrared light carrying orbital angular momentum

Frequency up-conversion is an effective method of mid-infrared(MIR) detection by converting long-wavelength photons to the visible domain, where efficient detectors are readily available. Here, we generate MIR light carrying orbital angular momentum(OAM) from a difference frequency generation process and perform up-conversion on it via sum frequency conversion in a bulk quasi-phase-matching crystal. The maximum quantum conversion efficiencies from MIR to visible are 34.0%, 10.4%, and 3.5% for light with topological charges of 0, 1, and 2, respectively, achieved by utilizing an optimized strong pump light. We also verify the OAM conservation with a specially designed interferometer, and the results agree well with the numerical simulations. Our study opens up the possibilities for generating, manipulating, and detecting MIR light that carries OAM, and will have great potential for optical communications and remote sensing in the MIR regime.

Generation of broadly tunable picosecond mid-infrared laser and sensitive detection of a mid-infrared signal by parametric frequency up-conversion in MgO:LiNbO_3 optical parametric amplifiers

Picosecond optical parametric generation and amplification in the near-infrared region within 1.361-1.656 μm and the mid-infrared region within 2.976-4.875 μm is constructed on the basis of bulk MgO：LiNbO 3 crystals pumped at 1.064 μm.The maximum pulse energy reaches 1.3 mJ at 1.464 μm and 0.47 mJ at 3.894 μm,corresponding to a pumpto-idler photon conversion efficiency of 25%.By seeding the hard-to-measure mid-infrared radiation as the idler in the optical parametric amplification and measuring the amplified and frequency up-converted signal in the near-infrared or even visible region,one can measure very week mid-infrared radiation with ordinary detectors,which are insensitive to mid-infrared radiation,with a very high gain.A maximum gain factor of about 7 脳 10 7 is achieved at the mid-infrared wavelength of 3.374 μm and the corresponding energy detection limit is as low as about 390 aJ per pulse.

Rapid Detection of Accelerants in Fire Debris Using a Field Portable Mid-Infrared Quantum Cascade Laser Based Analyzer

Arson presents a challenging crime scene for fire investigators worldwide. Key to the investigation of suspected arson cases is the analysis of fire debris for the presence of accelerants or ignitable liquids. This study has investigated the application and method development of vapor phase mid-Infrared (mid-IR) spectroscopy using a field portable quantum cascade laser (QCL) based system for the detection and identification of accelerant residues such as gasoline, diesel, and ethanol in fire debris. A searchable spectral library of various ignitable fluids and fuel components measured in the vapor phase was constructed that allowed for real-time identification of accelerants present in samples using software developed in-house. Measurement of vapors collected from paper material that had been doused with an accelerant followed by controlled burning and then extinguished with water showed that positive identification could be achieved for gasoline, diesel, and ethanol. This vapor phase mid-IR QCL method is rapid, easy to use, and has the sensitivity and discrimination capability that make it well suited for non-destructive crime scene sample analysis. Sampling and measurement can be performed in minutes with this 7.5 kg instrument. This vibrational spectroscopic method required no time-consuming sample pretreatment or complicated solvent extraction procedure. The results of this initial feasibility study demonstrate that this portable fire debris analyzer would greatly benefit arson investigators performing analysis on-site.

Quantitative Detection Model of Pernicious Gases in Pig House Based on BP Neural Network

To find a neural network model suitable to identify the concentration of mixed pernicious gases in pig house, the quantitative detection model of pernicious gases in pig house was set up based on BP （ Back propagation） neural network. The BP neural network was trained separately by the three functions, trainbr, traingdm and trainlm, in order to identify the concentration of mixed pernicious gases composed of ammonia gas and hepatic gas. The neural network toolbox in MATLAB software was used to simulate the detection. The results showed that the neural network trained by trainbr function has high average identification accuracy and faster detection speed, and it is also insensitive to noise; therefore, it is suitable to identify the concentration of pemidous gases in pig house. These data provide a reference for intelligent monitoring of pemicious gases in pigsty.

Wide dynamic detection range of methane gas based on enhanced cavity absorption spectroscopy

Integrated cavity output spectroscopy(ICOS) is an effective technique in trace gase detection.The strong absorption due to the long optical path of this method makes it challenging in the application scenes that have large gas concentration fluctuation,especially when the gas concentration is high.In this paper,we demonstrate an extension of the dynamic range of ICOS by using a detuned laser combined with an off-axis integrating cavity.With this,we improve the upper limit of the dynamic detection range from 0.1%(1000 ppm) to 20% of the gas concentration.This method provides a way of using ICOS in the applications with unpredictable gas concentrations such as gas leak detection,ocean acidification,carbon sequestration,etc.

Preparation of polythiophene/WO_3 organic-inorganic hybrids and their gas sensing properties for NO_2 detection at low temperature

Polythiophene/WO3（PTP/WO3）organic-inorganic hybrids were synthesized by an in situ chemical oxidative polymerization method,and char- acterized by X-ray diffraction（XRD）,transmission electron microscopy（TEM）and thermo-gravimetric analysis（TGA）.The Polythiophene/ WO3 hybrids have higher thermal stability than pure polythiophene,which is beneficial to potential application as chemical sensors.Gas sensing measurements demonstrate that the gas sensor based on the Polythiophene/WO3 hybrids has high response and good selectivity for de- tecting NO2 of ppm level at low temperature.Both the operating temperature and PTP contents have an influence on the response of PTP/WO3 hybrids to NO2.The 10 wt%PTP/WO3 hybrid showed the highest response at low operating temperature of 70-C.It is expected that the PTP/WO3 hybrids can be potentially used as gas sensor material for detecting the low concentration of NO2 at low temperature.

Gas concentration monitoring system for small and medium-sized coal mines based on gas-sensing detection and single-chip control

This paper is aimed at the actual conditions of disaster caused by gas in small and medium-sized coal mines. A new gas concentration monitoring system for coal mines is developed on the basis of gas-sensing detection and single-chip control. The monitoring system uses the tin oxide as the main material of N-type semiconductor gas sensors, be- cause it has good sensitive characteristics for the flammable and explosive gas （ such as methane, carbon monoxide）. The QM-N5-semiconductor gas sensor is adopted to detect the output values of the resistance under the different gas con- centrations. The system, designedly, takes the AT89C51 digital chip as the core of the circuit processing hardware structure to analyze and judge the input values of the resistance, and then achieve the control and alarm for going beyond the limit of gas concentration. The gas concentration monitoring system has man）, advantages including simple in struc- ture, fast response time, stable performance and low cost. Thus, it can be widely used to monitor gas concentration and provide early wamings in small and medium-sized coal mines.

SELECTIVE SULFUR DIOXIDE DETERMINATION BY GAS DIFFUSION FLOW INJECTION ANALYSIS WITH CHEMILUMINESCENT DETECTION

Sulfur dioxide has been found to decrease the chemiluminescence of luminol-iodine system.A new determination method for sulfur dioxide in atmosphere is developed by applying this reaction to a flow injection gas diffusion separation system.This permits the determination of sulfur dioxide selectively and rapidly.

Detection and analysis of gas tightness of continuous annealing furnaces

When a cold rolled strip is being treated in a continuous annealing furnace which is full of protective gas, the gas tightness of the furnace body, the connected facilities and the gas channels become an important indicator that directly affects the product＇s surface quality and shows the technical level of the design, the manufacture and the installation. By considering the problems of the gas tightness of a vertical annealing furnace in the installation and maintenance, this thesis evaluates the gas tightness indicator and gas tightness related level of the furnace body and the circulation duct, while studying and analyzing the technologies of negative-pressure leak detection and sealing.

A gas kick early detection method outside riser based on Doppler ultrasonic wave during deepwater drilling

The feasibility of gas kick early detection outside the riser was analyzed based on gas-liquid multiphase flow theory.Then an experimental platform for gas kick early detection based on Doppler ultrasonic wave was established and the propagation experiments in two-phase flow of gas-water(sucrose solutions)were conducted.The time and frequency domains of the Doppler ultrasonic wave signals during the experiments were analyzed.The results show that:(1)No matter the pump was on or off,the detected average Doppler ultrasonic signal voltage increased first and then decreased with the increase of the gas void fraction,and had a quadratic function relation with gas void fraction,so the average voltage change of the monitored signals can be used to deduce the approximate gas void fraction.The Doppler ultrasonic wave signal voltage was significantly reduced in magnitude and variation in the solution with higher viscosity,and the viscosity has stronger impact on the magnitude of signal than density.(2)When the pump was stopped,the Doppler shift increased with the increase of gas void fraction,and the two showed a nearly linear relation,so the detected amount of Doppler shift can reflect the variation of gas void fraction quantitatively.When the pump was on,the sound energy produced by frequency converter had a more significant impact on amplitude spectrum than gas void fraction,so it is impossible to determine whether gas kick occurs by frequency domain signal analysis.(3)This method is a non-contact measurement,with no contact with the drilling fluid and no disruption to the drilling operation.It can quantitatively characterize the gas void fraction according to the change of Doppler ultrasonic signal,enabling earlier detection of gas kick.

Test on oxygen and benzene contents in gasoline by mid-infrared spectroscopy

This paper aims at testing oxygen and benzene contents in gasoline by mid-infrared spectroscopy.The experimental results prove that infrared spectroscopy(IR)is reliable.Compared with gas chromatography(GC)technology,this paper draws a conclusion that IR has several advantages,including rapid analysis,excellent repeatability and low analysis cost.

Hydrocarbon detections using multi-attributes based quantum neural networks in a tight sandstone gas reservoir in the Sichuan Basin, China

A direct hydrocarbon detection is performed by using multi-attributes based quantum neural networks with gas fields.The proposed multi-attributes based quantum neural networks for hydrocarbon detection use data clustering and local wave decomposition based seismic attenuation characteristics,relative wave impedance features of prestack seismic data as the selected multiple attributes for one tight sandstone gas reservoir and further employ principal component analysis combined with quantum neural networks for giving the distinguishing results of the weak responses of the gas reservoir,which is hard to detect by using the conventional technologies.For the seismic data from a tight sandstone gas reservoir in the Sichuan basin,China,we found that multiattributes based quantum neural networks can effectively capture the weak seismic responses features associated with gas saturation in the gas reservoir.This study is hoped to be useful as an aid for hydrocarbon detections for the gas reservoir with the characteristics of the weak seismic responses by the complement of the multiattributes based quantum neural networks.

Intra-Cavity Absorption Sensors for Gas Detection Using Wavelength Sweep Technique

Wavelength sweep technique （WST） is introduced into intra-cavity fiber laser （ICFL） for low concentration gas detection. The limitation induced by noise can be eliminated using this method, and the performance of the system is improved. The sensitivity of the system is reduced to less than 300 ppm. With WST, sweeping characteristic of the ICFL can be described according to known gas absorption spectra.

Rock physics modeling of heterogeneous carbonatereservoirs： porosity estimation and hydrocarbon detection

In heterogeneous natural gas reservoirs, gas is generally present as small patchlike pockets embedded in the water-saturated host matrix. This type of heterogeneity, also called "patchy saturation", causes significant seismic velocity dispersion and attenuation. To establish the relation between seismic response and type of fluids, we designed a rock physics model for carbonates. First, we performed CT scanning and analysis of the fluid distribution in the partially saturated rocks. Then, we predicted the quantitative relation between the wave response at different frequency ranges and the basic lithological properties and pore fluids. A rock physics template was constructed based on thin section analysis of pore structures and seismic inversion. This approach was applied to the limestone gas reservoirs of the right bank block of the Amu Darya River. Based on poststack wave impedance and prestack elastic parameter inversions, the seismic data were used to estimate rock porosity and gas saturation. The model results were in good agreement with the production regime of the wells.

A proposed NMR solution for multi-phase flow fluid detection

In the petroleum industry,detection of multi-phase fluid flow is very important in both surface and down-hole measurements.Accurate measurement of high rate of water or gas multi-phase flow has always been an academic and industrial focus.NMR is an efficient and accurate technique for the detection of fluids;it is widely used in the determination of fluid compositions and properties.This paper is aimed to quantitatively detect multi-phase flow in oil and gas wells and pipelines and to propose an innovative method for online nuclear magnetic resonance(NMR)detection.The online NMR data acquisition,processing and interpretation methods are proposed to fill the blank of traditional methods.A full-bore straight tube design without pressure drop,a Halbach magnet structure design with zero magnetic leakage outside the probe,a separate antenna structure design without flowing effects on NMR measurement and automatic control technology will achieve unattended operation.Through the innovation of this work,the application of NMR for the real-time and quantitative detection of multi-phase flow in oil and gas wells and pipelines can be implemented.

The Sensitive Properties of Hydrate Reservoirs Based on Seismic Stereoscopic Detection Technology

Higher-precision determinations of hydrate reservoirs, hydrate saturation levels and storage estimations are important for guaranteeing the ability to continuously research, develop and utilize natural gas hydrate resources in China. With seismic stereoscopic detection technology, which fully combines the advantages of different seismic detection models, hydrate formation layers can be observed with multiangle, wide-azimuth, wide-band data with a high precision. This technique provides more reliable data for analyzing the distribution characteristics of gas hydrate reservoirs, establishing velocity models, and studying the hydrate-sensitive properties of petrophysical parameters;these data are of great significance for the exploration and development of natural gas hydrate resources. Based on a velocity model obtained from the analysis of horizontal streamer velocity data in the hydrate-bearing area of the Shenhu Sea, this paper uses three VCs(longitudinal spacing of 25 m) and four OBSs(transverse spacing of 200 m) to jointly detect seismic datasets consisting of wave points based on an inversion of traveltime imaging sections. Accordingly, by comparing the differences between the seismic phases in the original data and the forward-modeled seismic phases, multiangle coverage constraint corrections are applied to the initial velocity model, and the initial model is further optimized, thereby improving the imaging quality of the streamer data. Petrophysical elastic parameters are the physical parameters that are most directly and closely related to rock formations and reservoir physical properties. Based on the optimized velocity model, the rock elastic hydrate-sensitive parameters of the hydrate reservoirs in the study area are inverted, and the sensitivities of the petrophysical parameters to natural gas hydrates are investigated. According to an analysis of the inversion results obtained from these sensitive parameters, λρ, Vp and λμ are simultaneously controlled by the bulk modulus and shear modulus, while Vs and μρ are controlled only by the shear modulus, and the latter two parameters are less sensitive to hydrate-bearing layers. The bulk modulus is speculated to be more sensitive than the shear modulus to hydrates. In other words, estimating the specific gravity of the shear modulus among the combined parameters can affect the results from the combined elastic parameters regarding hydrate reservoirs.

A risk-based methodology for the optimal placement of hazardous gas detectors

Hazardous gas detection systems play an important role in preventing catastrophic gas-related accidents in process industries. Even though effective detection technology currently exists for hazardous gas releases and a majority of process installations have a large number of sensitive detectors in place, the actual operating performance of gas detection systems still does not meet the expected requirements. In this paper, a riskbased methodology is proposed to optimize the placement of hazardous gas detectors. The methodology includes three main steps, namely, the establishment of representative leak scenarios, computational fluid dynamics(CFD)-based gas dispersion modeling, and the establishment of an optimized solution. Based on the combination of gas leak probability and joint distribution probability of wind velocity and wind direction, a quantitative filtering approach is presented to select representative leak scenarios from all potential scenarios. The commercial code ANSYS-FLUENT is used to estimate the consequence of hazardous gas dispersions under various leak and environmental conditions. A stochastic mixed-integer linear programming formulation with the objective of minimizing the total leak risk across all representative leak scenarios is proposed, and the greedy dropping heuristic algorithm(GDHA) is used to solve the optimization model. Finally, a practical application of the methodology is performed to validate its effectiveness for the optimal design of a gas detector system in a high-sulfur natural gas purification plant in Chongqing, China. The results show that an appropriate number of gas detectors with optimal cost-effectiveness can be obtained, and the total leak risk across all potential scenarios can be substantially reduced. This methodology provides an effective approach to guide the optimal placement of pointtype gas detection systems involved with either single or mixed gas releases.

Using acoustic technique to detect leakage in city gas pipelines

For solving the difficult problem of leakage detection in city gas pipelines, a method using acoustic technique based on instantaneous energy (IE) distribution and correlation analysis was proposed. Firstly, the basic theory of leakage detection and location was introduced. Then the physical relationship between instantaneous energy and structural state variation of a system was analyzed theoretically. With HILBERT-HUANG transformation (HHT), the instantaneous energy distribution feature of an unstable acoustic signal was obtained. According to the relative contribution method of the instantaneous energy, the noise in signal was eliminated effectively. Furthermore, in order to judge the leakage, the typical characteristic of the instantaneous energy of signal in the input and output end was discussed using correlative analysis. A number of experiments were carried out to classify the leakage from normal operations, and the results show that the leakages are successfully detected and the average recognition rate reaches 93.3% among three group samples. It is shown that the method using acoustic technique with IED and correlative analysis is effective and it may be referred in other pipelines.