Unprecedented Reversible Real-Time Luminescent Sensing of H₂S in the Gas Phase

Abstract

Hydrogen sulfide monitoring has become essential in the natural gas industry, biogas production, wastewater treatment plants, paper mills, sewers, and landfills of waste due to its toxic, irritating, extremely flammable, and corrosive features. However, each of the current monitoring technologies (gas chromatography, lead acetate tape, electrochemical, UV and NIR absorption) has its own limitations. Furthermore, the existing luminescent molecular probes for H 2 S cannot monitor it continuously due to the irreversibility of their reaction with the analyte. Herein, we report the development and application of the first reversible H 2 S luminescent sensor. The sensing layer capitalizes on the highly photooxidizing phosphorescent [bis(1,10-phenanthroline)-(1,4,5,8-tetraazaphenanthrene)]ruthenium(II) dication immobilized on alkali-treated silica microspheres, interrogated with a dedicated fiberoptic phase-sensitive luminometer. The chemosensing mechanism is a fully reversible electron transfer from the analyte to the photoexcited dye. The H 2 S optosensor exhibits a 0.34−50 ppmv dynamic range, a limit of detection equal to 0.025 ppmv, repeatability, and reproducibility better than 3.2%, plus response and recovery times (t 90 and t −90 ) shorter than 240 s. The H 2 S luminescent sensor performance has been verified for more than six months in a biomethane production plant, showing an excellent stability with automatic daily maintenance.

Reaction-Based Luminescent Probes for Reactive Sulfur, Oxygen, and Nitrogen Species: Analytical Techniques and Recent Progress

“…Luminescent europium and terbium complexes exhibit long-lived emissive peaks in the range of 490–700 nm, and europium ,, and terbium , probes based on copper precipitation have been reported. Luminescent iridium , and ruthenium , complexes have also been used to make hydrogen sulfide probes. Metal complexes such as these open up intriguing opportunities such as electrochemiluminescent sensing or reversible sensing using electron transfer reactions .…”

Modeling, instrumentation, automation, and optimization of water resource recovery facilities (2019) DIRECT

“…Kõrgmaa et al (2019) reported on the use of sensor‐based automation to improve sludge volume index in several water reclamation plants and process consistency. Urriza‐Arsuaga, Bedoya, and Orellana (2019) focused on improving the reliability of continuous monitoring technology for hydrogen sulfide which otherwise was difficult to achieve due to numerous constraints. A new sensor was developed and applied with favorable results.…”

Corrosion Sensors for Structural Health Monitoring of Oil and Natural Gas Infrastructure: A Review

“…Because dissolved CO 2 can reduce the solution pH, CO 2 sensors also employ pH indicators (colorimetric or fluorescent dyes) within various sensing layers such as silica gel coating, polymer matrix with quantum dots, and sol–gel matrix with silica nanoparticles [172,173,174,175,176,177]. H 2 S monitoring often utilizes reactive sensing materials such as Ag [178,179], Cu [180,181], ZnO [182,183], CuO doped SnO 2 [184], CdO [185], and fluorescent or luminescent indicators [186,187,188]. More H 2 S sensitive materials can be found in References [189,190].…”