Cu-based metal-organic framework (MOF) microdevices are applied in sampling and preconcentration of nerve agents (NAs) diluted in gaseous streams. An in situ electrochemical-assisted synthesis of a Cu-benzene-1,3,5-tricarboxylate (BTC) thick film is carried out to functionalize a Cu-modified glass substrate. This simple, rapid, reproducible, and easy-to-integrate MOF synthesis approach enables the microfabrication of functional micro-preconcentrators with a large Brunauer-Emmett-Teller (BET) surface area (above 2000 cm2) and an active pore volume (above 90 nL) for the efficient adsorption of nerve agent molecules along the microfluidic channel 2.5 cm in length. The equilibrium adsorption capacity of the bulk material has been characterized through thermogravimetric analysis after exposure to controlled atmospheres of a sarin gas surrogate, dimethyl methylphosphonate (DMMP), in both dry and humid conditions (30% RH at 293 K). Breakthrough tests at the ppm level (162 mg/m3) reveal equilibrium adsorption capacities up to 691 mg/g. The preconcentration performance of such μ-devices when dealing with highly diluted surrogate atmosphere, i.e., 520 ppbV (2.6 mg/m3) at 298 K, leads to preconcentration coefficients up to 171 for sample volume up to 600 STP cm3. We demonstrate the potentialities of Cu-BTC micro-preconcentrators as smart first responder tools for "on-field" detection of nerve agents in the gas phase at relevant conditions.

Three-dimensional mathematical model was developed for a rectangular TE _10n microwave heating cavity system, working at 2.45 GHz. Energy/heat, momentum equations were solved together with Maxwell's electromagnetic field equations using COMSOL MULTIPHYSICS® simulation environment. The dielectric properties, ε' and ε'', of NaY zeolite (Si/Al = 2.5) were evaluated as a function of temperature. Considering these values, the microwave heating of a porous fixed-bed made of dry NaY zeolite was simulated. Electric field distribution, axial and radial temperature profiles and temperature evolution with time were obtained. The zeolite fixed bed was heated up to 180 °C in 5 min, with 30 W power. The fixed-bed temperature evolution under non-steady state conditions showed the same trend as the one observed experimentally with only an average deviation of 10.3%. The model was used to predict microwave heating of other materials improving energy efficiency of the microwave cavity. Furthermore, the developed model was able to predict thermal runaway for zeolites.

A series of ruthenium-doped strontium titanate (SrTiO₃) perovskite catalysts were synthesized by conventional and microwave-assisted hydrothermal methods. The structure was analyzed by X-Ray diffraction (XRD) confirming the formation of the perovskite phase with some TiO₂ anatase phase in all the catalysts. Microwave irradiation decreases the temperature and time of synthesis from 220 °C for 24 h (conventional heating) to 180 °C for 1h, without affecting the formation of perovskite. A 7 wt. % ruthenium-doped SrTiO₃ catalyst showed the best dielectric properties, and thus its catalytic activity was evaluated for the methane dry reforming reaction under microwave heating in a custom fixed-bed quartz reactor. Microwave power, CH₄:CO₂ vol. % feed ratio and gas hourly space velocity (GHSV) were varied in order to determine the best conditions for performing dry reforming with high reactants conversions and H₂/CO ratio. Stable maximum CH₄ and CO₂ conversions of ∼99.5% and ∼94%, respectively, at H₂/CO ∼0.9 were possible to reach with the 7 wt. % ruthenium-doped SrTiO₃ catalyst exposed to maximum temperatures in the vicinity of 940 °C. A comparative theoretical scale-up study shows significant improvement in H₂ production capability in the case of the perovskite catalyst compared to carbon-based catalysts.

The release of nanosized particles from fluidized beds of ceramic oxide nanopowders, namely, TiO₂ (P25), Al₂O₃ (AluC) and SiO₂ (A130) has been assessed for the first time. Previous models and experiments for processing engineered nanoparticles (ENP) using fluidized beds reported only the formation of micron-sized cluster agglomerates in the gas phase. In this work, aerosol spectrometry techniques such as scanning mobility particle sizing (SMPS) and optical particle counting (OPC) have been combined with powder technologies, such as the borescope high-speed camera system, to determine the particle size distribution from 5 nm to 1 mm above a fluidized bed. Furthermore, the morphology of nanoparticulate aerosol at different locations in the bed was determined by offline electron microscopy. The results demonstrate that free nano- and micron-sized particles are released from fluidized beds. Since the structures found above the bed are also expected to be present within fluidized beds, a revision of existing nanoparticle fluidization models, and improved safety and control measures in reactors for gas-phase ENP processing are needed to avoid nanoparticle release.