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).

Fast Dynamic Synthesis of MIL-68(In) Thin Films in High Optical Quality for Optical Cavity Sensing.

Fabrication of metal-organic framework (MOF) thin films rigidly anchored on suitable substrates is a crucial prerequisite for the integration of these porous hybrid materials into electronic and optical devices. Thus, far, the structural variety for MOF thin films available through layer-by-layer deposition was limited, as the preparation of those surface-anchored metal-organic frameworks (SURMOFs) has several requirements: mild conditions, low temperatures, day-long reaction times, and nonaggressive solvents. We herein present a fast method for the preparation of the MIL SURMOF on Au-surfaces under rather harsh conditions: Using a dynamic layer-by-layer synthesis for MIL-68(In), thin films of adjustable thickness between 50 and 2000 nm could be deposited within only 60 min. The MIL-68(In) thin film growth was monitored in situ using a quartz crystal microbalance. In-plane X-ray diffraction revealed oriented MIL-68(In) growth with the pore-channels of this interesting MOF aligned parallel to the support. Scanning electron microscopy data demonstrated an extraordinarily low roughness of the MIL-68(In) thin films. Mechanical properties and lateral homogeneity of the layer were probed through nanoindentation. These thin films showed extremely high optical quality. By applying a poly(methyl methacrylate) layer and further depositing an Au-mirror to the top, a MOF optical cavity was fabricated that can be used as a Fabry-Perot interferometer. The MIL-68(In)-based cavity showed a series of sharp resonances in the ultraviolet-visible regime. Changes in the refractive index of MIL-68(In) caused by exposure to volatile compounds led to pronounced position shifts of the resonances. Thus, these cavities are well suited to be used as optical read-out sensors.

Hollow nano-CaCO3's VOC sensing properties: A DFT calculation and experimental assessments.

Air is the most critical and necessary for life, and air quality significantly impacts people's health. Both indoor and outdoor pollution frequently contain volatile organic compounds (VOCs). Such contaminants provide immediate or long-term health risks to the living system. The present study investigates sorption characteristics of VOCs on hollow nano calcite (CaCO3) particles with 250 nm and 40 nm pore sizes to remove from the air ambient using the quartz crystal microbalance (QCM) technique at room temperature both experimentally and theoretically. The results were supported by density functional theory (DFT), and adsorption-desorption characteristics were studied with Langmuir adsorption isotherms. The QCM measurements showed a stable signal without having hysteresis, and the response of polar VOCs on hollow nano-CaCO3 particles such as ethanol, propanol, and humidity with higher polarity was less compared to solvents such as chloroform and dichloromethane, which revealed that the surfaces of CaCO3 particles have mostly non-polar properties. CaCO3 surface and VOC molecule interactions overlap with the Langmuir model. With DFT calculations, VOC and water molecule adsorption changes the CaCO3 Egap. Our findings show that the ΔEgap values increase as chloroform > dichloromethane > propanol > ethanol > water. This order suggests that the sensing response of the hollow CaCO3 structure is linearly proportional to the adsorption energies of VOC and water. The linear adsorption characteristics, high sensing response, and short recovery time illustrated that the newly synthesized nano-CaCO3 could be implemented as a new VOC adsorbent material for health, environmental sustainability, and in vitro microbiome cultures.

VOC Mixture Sensing with a MOF Film Sensor Array: Detection and Discrimination of Xylene Isomers and Their Ternary Blends.

Detection and recognition of volatile organic compounds (VOCs) are crucial in many applications. While pure VOCs can be detected by various sensors, the discrimination of VOCs in mixtures, especially of similar molecules, is hindered by cross-sensitivities. Isomer identification in mixtures is even harder. Metal-organic frameworks (MOFs) with their well-defined, nanoporous, and versatile structures have the potential to improve the VOC sensing performance by tailoring the adsorption affinities. Here, we detect and identify ternary xylene isomer mixtures by using an array of six gravimetric, quartz crystal microbalance (QCM)-based sensors coated with selected MOF films with different isomer affinities. We use classical molecular simulations to provide insights into the sensing mechanism. In addition to the attractive interaction between the analytes and the MOF film, the isomer discrimination is caused by the rigid crystalline framework sterically controlling the access of the isomers to different adsorption sites in the MOFs. The sensor array has a very low limit of detection of 1 ppm for each pure isomer and allows the isomer discrimination in mixtures. At 100 ppm, 16 different ternary o-p-m-xylene mixtures were identified with high classification accuracy (96.5%). This work shows the unprecedented performance of MOF-sensor arrays, also referred to as MOF-electronic nose (MOF-e-nose), for sensing VOC mixtures. Based on the study, guidelines for detecting and discriminating complex mixtures of volatile molecules are also provided.

A photoprogrammable electronic nose with switchable selectivity for VOCs using MOF films.

Advanced analytical applications require smart materials and sensor systems that are able to adapt or be configured to specific tasks. Based on reversible photochemistry in nanoporous materials, we present a sensor array with a selectivity that is reversibly controlled by light irradiation. The active material of the sensor array, or electronic nose (e-nose), is based on metal-organic frameworks (MOFs) with photoresponsive fluorinated azobenzene groups that can be optically switched between their trans and cis state. By irradiation with light of different wavelengths, the trans-cis ratio can be modulated. Here we use four trans-cis values as defined states and employ a four-channel quartz-crystal microbalance for gravimetrically monitoring the molecular uptake by the MOF films. We apply the photoprogrammable e-nose to the sensing of different volatile organic compounds (VOCs) and analyze the sensor array data with simple machine-learning algorithms. When the sensor array is in a state with all sensors either in the same trans- or cis-rich state, cross-sensitivity between the analytes occurs and the classification accuracy is not ideal. Remarkably, the VOC molecules between which the sensor array shows cross-sensitivity vary by switching the entire sensor array from trans to cis. By selectively programming the e-nose with light of different colors, each sensor exhibits a different isomer ratio and thus a different VOC affinity, based on the polarity difference between the trans- and cis-azobenzenes. In such photoprogrammed state, the cross-sensitivity is reduced and the selectivity is enhanced, so that the e-nose can perfectly identify the tested VOCs. This work demonstrates for the first time the potential of photoswitchable and thus optically configurable materials as active sensing material in an e-nose for intelligent molecular sensing. The concept is not limited to QCM-based azobenzene-MOF sensors and can also be applied to diverse sensing materials and photoswitches.

An Enantioselective e-Nose: An Array of Nanoporous Homochiral MOF Films for Stereospecific Sensing of Chiral Odors.

Chirality is essential in nature and often pivotal for biological information transfer, for example, via odor messenger molecules. While the human nose can distinguish the enantiomers of many chiral odors, the technical realization by an artificial sensor or an electronic nose, e-nose, remains a challenge. Herein, we present an array of six sensors coated with nanoporous metal-organic framework (MOF) films of different homochiral and achiral structures, working as an enantioselective e-nose. While the achiral-MOF-film sensors show identical responses for both isomers of one chiral odor molecule, the responses of the homochiral MOF films differ for different enantiomers. By machine learning algorithms, the combined array data allow the stereoselective identification of all compounds, here tested for five pairs of chiral odor molecules. We foresee the chiral-MOF-e-nose, able to enantioselectively detect and discriminate chiral odors, to be a powerful approach towards advanced odor sensing.

Humidity adsorption kinetics of a trypsin gel film.

This study focuses on the humidity adsorption kinetics of an isopropanol-induced and pH-triggered bovine pancreatic trypsin gel (BPTG). The BPTG was adsorbed on a gold coated Quartz Crystal Microbalance (QCM) substrate with a thickness of 376 nm. The morphology of the film was characterized using Atomic Force Microscopy (AFM). QCM was used to investigate the humidity sensing properties of the BPTG film. The response of the humidity sensor was explained using the Langmuir model. The average values of adsorption and desorption rates between 11% RH (relative humidity) and 97% RH were calculated as 2482.5 M(-1) s(-1) and 0.02 s(-1), respectively. The equilibrium constant and average Gibbs Free Energy of humidity adsorption and desorption cycles were obtained as 133,000 and -11.8 kJ/mol, respectively.

Humidity sensing properties of ZnO-based fibers by electrospinning.

Zinc oxide (ZnO) based fibers with a diameter of 80-100 nm were prepared by electrospinning. Polyvinyl alcohol (PVA) and zinc acetate dihydrate were dissolved in water and the polymer/salt solution was electrospun at 2.5 kV cm(-1). The resulting electrospun fibers were subjected to calcination at 500°C for 2h to obtain ZnO-based fibers. Humidity sensing properties of the fiber mats were investigated by quartz crystal microbalance (QCM) method and electrical measurements. The adsorption kinetics under constant relative humidity (RH) between 10% and 90% were explained using Langmuir adsorption model. Results of the measurements showed that ZnO-based fibers were found to be promising candidate for humidity sensing applications at room temperature.

Humidity adsorption kinetics of calix[4]arene derivatives measured using QCM technique.

This study focuses on the characterization of sulphonated calix[4]arene derivative films coated on a quartz substrate with a thickness of 40 nm by spin coating method for humidity detection. The humidity adsorption kinetics of the sulphonated calix[4]arene films was investigated by quartz crystal microbalance (QCM) technique. The Langmuir model was used to determine the adsorption rates and Gibbs free energy for various relative humidities between 11% and 97%. Our reproducible experimental results show that suphonated calix[4]arene films have a great potential for humidity sensing applications at room temperature operations.

Scanning probe oxidation lithography on Ta thin films.

A Semi-Contact Scanning Probe Lithography Technique (SC-SPL) has been applied to create nano-oxide patterns on Ta thin films grown by DC magnetron sputtering method on SiO2/Si substrates. The height and linewidth profiles of nano-oxide lines created by a conductive AFM tip on Ta film surfaces were measured as a function of applied voltage, oxidation time, humidity, and tip apex curvature. The AFM surface measurements show that the height of the oxides increases linearly with increasing voltage; but there was no oxide growth, when less than 4 V was applied even at 85% relative humidity. Electrical measurements were performed and the resistivities of the TaOx layer and Ta film were obtained as 5.76 x 10(8) and 1.4 x 10(-5) Ohm-cm, respectively.