Surface-enhanced Raman scattering (SERS) is a powerful spectroscopic technique for selective detection and quantification of molecules at extremely low concentrations. However, practical SERS applications for gaseous chemicals with small cross section is still in its early stages. We herein report a plasmonic-sorbent thin-film platform with integrated Raman internal standard with outstanding SERS sensing capabilities for chemical warfare agents (CWA) simulants. The thin film is constituted of close-packed core–shell [email protected] nanorods individually encapsulated within a ZIF-8 framework ([email protected]@ZIF-8). While the [email protected] nanoparticles amplify the Raman signal of molecules located near their surface, the ZIF-8 framework plays a key role in the trapping of the dimethyl methylphosphonate (DMMP) or 2-chloroethyl ethyl sulfide (CEES) from the gas phase as well as Raman internal standard. The underlying adsorption mechanism of the molecules within the ZIF-8 framework as well as the interaction between DMMP and Ag surface are investigated by computational simulations. Outstanding SERS sensing capabilities of [email protected]@ZIF-8 thin films, in terms of response time, quantification limit, reproducibility, and recyclability, are demonstrated for dimethyl methylphosphonate (DMMP) and 2-chloroethyl ethyl sulfide (CEES), selected as CWA simulants of sarin gas and mustard gas, respectively. A limit of detection (LOD) of 0.2 ppbV is reported for DMMP. Additionally, experiments performed with portable Raman equipment detect 2.5 ppmV for DMMP in ambient air and 76 ppbV for CEES in N₂, with response times of 21 and 54 s, respectively. This proof of concept opens the door for handheld SERS-based gas sensing at ultralow concentrations in practical applications, such as homeland security, critical infrastructure protection, chemical process monitoring, or personalized medicine.

Research in solid-gas heterogeneous catalytic processes is typically aimed toward optimization of catalyst composition to achieve a higher conversion and, especially, a higher selectivity. However, even with the most selective catalysts, an upper limit is found: Above a certain temperature, gas-phase reactions become important and their effects cannot be neglected. Here, we apply a microwave field to a catalyst-support ensemble capable of direct microwave heating (MWH). We have taken extra precautions to ensure that (i) the solid phase is free from significant hot spots and (ii) an accurate estimation of both solid and gas temperatures is obtained. MWH allows operating with a catalyst that is significantly hotter than the surrounding gas, achieving a high conversion on the catalyst while reducing undesired homogeneous reactions. We demonstrate the concept with the CO₂-mediated oxidative dehydrogenation of isobutane, but it can be applied to any system with significant undesired homogeneous contributions.

The surface of ordered mesoporous (MCM‐48) silica has been subjected to covalent grafting with silane molecules containing one to three amino groups. The dielectric properties of the materials were studied in detail, and the functionalized materials were used for CO₂ adsorption at room temperature, followed by regeneration under either conventional heating or microwave irradiation. It has been found that, as the intensity of functionalization with amino groups increases (from mono‐ to tri‐amino silanes) both the CO₂ load and the dielectric response at microwave frequencies increase. In particular, functionalization with a tri‐amino silane derivative gave the highest CO₂ adsorption and the fastest microwave heating, resulting in a fourfold acceleration of adsorbent regeneration. The grafted material was fully stable for at least 20 adsorption‐regeneration cycles, making it an ideal candidate for microwave‐swing adsorption (MWSA) processes. © 2015 American Institute of Chemical Engineers AIChE J, 62: 547–555, 2016