Optimized Detection of Volatile Organic Compounds Utilizing Durable and Selective Arrays of Tailored UiO-66-X SURMOF Sensors.

Metal-organic frameworks (MOFs), with their well-defined and highly flexible nanoporous architectures, provide a material platform ideal for fabricating sensors. We demonstrate that the efficacy and specificity of detecting and differentiating volatile organic compounds (VOCs) can be significantly enhanced using a range of slightly varied MOFs. These variations are obtained via postsynthetic modification (PSM) of a primary framework. We alter the original MOF's guest adsorption affinities by incorporating functional groups into the MOF linkers, which yields subtle changes in responses. These responses are subsequently evaluated by using machine learning (ML) techniques. Under severe conditions, such as high humidity and acidic environments, sensor stability and lifespan are of utmost importance. The UiO-66-X MOFs demonstrate the necessary durability in acidic, neutral, and basic environments with pH values ranging from 2 to 11, thus surpassing most other similar materials. The UiO-66-NH2 thin films were deposited on quartz-crystal microbalance (QCM) sensors in a high-temperature QCM liquid cell using a layer-by-layer pump method. Three different, highly stable surface-anchored MOFs (SURMOFs) of UiO-66-X obtained via the PSM approach (X: NH2, Cl, and N3) were employed to fabricate arrays suitable for electronic nose applications. These fabricated sensors were tested for their capability to distinguish between eight VOCs. Data from the sensor array were processed using three distinct ML techniques: linear discriminant (LDA), nearest neighbor (k-NN), and neural network analysis methods. The discrimination accuracies achieved were nearly 100% at high concentrations and over 95% at lower concentrations (50-100 ppm).

Stability of Monolithic MOF Thin Films in Acidic and Alkaline Aqueous Media.

In the context of thin film nanotechnologies, metal-organic frameworks (MOFs) are currently intensively explored in the context of both, novel applications and as alternatives to existing materials. When it comes to applications under relatively harsh conditions, in several cases it has been noticed that the stability of MOF thin films deviates from the corresponding standard, powdery form of MOFs. Here, we subjected SURMOFs, surface-anchored MOF thin films, fabricated using layer-by layer methods, to a thorough characterization after exposure to different harsh aqueous environments. The stability of three prototypal SURMOFs, HKUST-1, ZIF-8, and UiO-66-NH2 was systematically investigated in acidic, neutral, and basic environments using X-ray diffraction and electron microscopy. While HKUST-1 films were rather unstable in aqueous media, ZIF-8 SURMOFs were preserved in alkaline environments when exposed for short periods of time, but in apparent contrast to results reported in the literature for the corresponding bulk powders- not stable in neutral and acidic environments. UiO-66-NH2 SURMOFs were found to be stable over a large window of pH values.

Efficient Fluoride Removal from Aqueous Solution Using Zirconium-Based Composite Nanofiber Membranes.

Herein, composite nanofiber membranes (CNMs) derived from UiO-66 and UiO-66-NH2 Zr-metal-organic frameworks (MOFs) were successfully prepared, and they exhibited high performance in adsorptive fluoride removal from aqueous media. The resultant CNMs were confirmed using different techniques, such as X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and Brunauer-Emmett-Teller (BET) in addition to Fourier-transform infrared spectroscopy (FTIR). The parameters that govern the fluoride adsorption were evaluated, including adsorbent dose, contact time, and pH value, in addition to initial concentration. The crystalline structures of CNMs exhibited high hydrothermal stability and remained intact after fluoride adsorption. It could also be observed that the adsorbent dose has a significant effect on fluoride removal at high alkaline values. The results show that UiO-66-NH2 CNM exhibited high fluoride removal due to electrostatic interactions that strongly existed between F- and metal sites in MOF in addition to hydrogen bonds formed with MOF amino groups. The fluoride removal efficiency reached 95% under optimal conditions of 20 mg L-1, pH of 8, and 40% adsorbent dose at 60 min. The results revealed that UiO-66-NH2 CNM possesses a high maximum adsorption capacity (95 mg L-1) over UiO-66 CNM (75 mg L-1), which exhibited better fitting with the pseudo-second-order model. Moreover, when the initial fluoride concentration increased from 20 to 100 mg/L, fluoride adsorption decreased by 57% (UiO-66 CNM) and 30% (UiO-66-NH2 CNM) after 60 min. After three cycles, CNM revealed the regeneration ability, demonstrating that UiO-66-NH2 CNMs are auspicious adsorbents for fluoride from an aqueous medium.