Studying ZIF-8 SURMOF Thin Films with a Langatate Crystal Microbalance: Single-Component Gas Adsorption Isotherms Measured at Elevated Temperatures and Pressures.

Characterizing the adsorption behavior of thin films at technical operation ranges is highly relevant in order to obtain appropriate experimental parameters, as well as to evaluate their possible integration in multiple applications. Nonetheless, gathering such experimental data is not a trivial task. In the case of metal-organic framework thin films, a particular interesting class of highly porous coatings, determination of adsorption isotherms at elevated temperatures and pressures is not commonly reported. Using a custom-designed langatate crystal microbalance following the principle for piezoelectric microbalances, but under harsher conditions, allowed us to present adsorption equilibrium measurements on a zeolitic imidazolate framework-8 (ZIF-8) surface-mounted metal-organic framework (SURMOF) thin film at temperatures between 35 and 100 °C and at a pressure range up to 10 bars. The layer-by-layer liquid-phase epitaxy approach was used to deposit ZIF-8 SURMOF thin films on langatate crystals. X-ray diffraction, infrared reflection absorption spectroscopy, and scanning electron microscopy combined with energy dispersive X-ray mapping were used to gather deeper information on the ZIF-8 thin film growth. Single-component isotherms were collected for different gases of practical interest, that is, CO2, C2H6, C2H4, C3H8, and C3H6. The measurements were obtained at 35, 50, 75, and 100 °C at a gauge pressure range up to 10 bars. The collected data showed a clear preferential adsorption of ethane over ethylene, whereas only a slight difference was found between propane and propylene. Additionally, the experimental data allowed for the determination of adsorption equilibrium constants and saturation loadings of the ZIF-8 material as a thin SURMOF film, which is of great importance for its integration in multiple applications, such as sensor devices or in membrane-based separation.

Crowd oil not crude oil.

Climate change represents an existential, global threat to humanity, yet its delocalized nature complicates climate action. Here, the authors propose retrofitting air conditioning units as integrated, scalable, and renewable-powered devices capable of decentralized CO2 conversion and energy democratization.

In Situ Multimodal 3D Chemical Imaging of a Hierarchically Structured Core@Shell Catalyst.

A Cu/ZnO/Al2O3@ZSM-5 core@shell catalyst active for one-step conversion of synthesis gas to dimethyl ether (DME) was imaged simultaneously and in situ using synchrotron-based micro X-ray fluorescence (µ-XRF), X-ray diffraction (µ-XRD), and scanning transmission X-ray microscopy (STXM) computed tomography (CT) with micrometer spatial resolution. An identical sample volume was imaged stepwise, first under oxidizing and reducing atmospheres (imitating calcination and activation processes), and then under model reaction conditions for DME synthesis (H2:CO:CO2 ratio of 16:8:1, up to 250 °C). The multimodal imaging methods offered insights into the active metal structure and speciation within the catalyst, and allowed imaging of both the catalyst core and zeolite shell in a single acquisition. Dispersion of nanosized Cu species was observed in the catalyst core during reduction, with formation of a metastable Cu+ phase at the core-shell interface. Under DME reaction conditions at 1 bar, the coexistence of Cu0 in the active catalyst core together with partially oxidized Cu species was unraveled. The zeolite shell and core-shell interface remained stable under all conditions, preserving the bifunctional nature of the catalyst. These observations are inaccessible using standard bulk techniques like X-ray absorption spectroscopy (XAS) and XRD, demonstrating the potential of multimodal in situ X-ray CT for characterization of hierarchically designed materials, which stand to benefit tremendously from such 3D spatially resolved measurements.

Stability of a Bifunctional Cu-Based Core@Zeolite Shell Catalyst for Dimethyl Ether Synthesis Under Redox Conditions Studied by Environmental Transmission Electron Microscopy and In Situ X-Ray Ptychography.

When using bifunctional core@shell catalysts, the stability of both the shell and core-shell interface is crucial for catalytic applications. In the present study, we elucidate the stability of a CuO/ZnO/Al2O3@ZSM-5 core@shell material, used for one-stage synthesis of dimethyl ether from synthesis gas. The catalyst stability was studied in a hierarchical manner by complementary environmental transmission electron microscopy (ETEM), scanning electron microscopy (SEM) and in situ hard X-ray ptychography with a specially designed in situ cell. Both reductive activation and reoxidation were applied. The core-shell interface was found to be stable during reducing and oxidizing treatment at 250°C as observed by ETEM and in situ X-ray ptychography, although strong changes occurred in the core on a 10 nm scale due to the reduction of copper oxide to metallic copper particles. At 350°C, in situ X-ray ptychography indicated the occurrence of structural changes also on the µm scale, i.e. the core material and parts of the shell undergo restructuring. Nevertheless, the crucial core-shell interface required for full bifunctionality appeared to remain stable. This study demonstrates the potential of these correlative in situ microscopy techniques for hierarchically designed catalysts.

Adsorption Device Based on a Langatate Crystal Microbalance for High Temperature High Pressure Gas Adsorption in Zeolite H-ZSM-5.

We present a high-temperature and high-pressure gas adsorption measurement device based on a high-frequency oscillating microbalance (5 MHz langatate crystal microbalance, LCM) and its use for gas adsorption measurements in zeolite H-ZSM-5. Prior to the adsorption measurements, zeolite H-ZSM-5 crystals were synthesized on the gold electrode in the center of the LCM, without covering the connection points of the gold electrodes to the oscillator, by the steam-assisted crystallization (SAC) method, so that the zeolite crystals remain attached to the oscillating microbalance while keeping good electroconductivity of the LCM during the adsorption measurements. Compared to a conventional quartz crystal microbalance (QCM) which is limited to temperatures below 80 °C, the LCM can realize the adsorption measurements in principle at temperatures as high as 200-300 °C (i.e., at or close to the reaction temperature of the target application of one-stage DME synthesis from the synthesis gas), owing to the absence of crystalline-phase transitions up to its melting point (1,470 °C). The system was applied to investigate the adsorption of CO2, H2O, methanol and dimethyl ether (DME), each in the gas phase, on zeolite H-ZSM-5 in the temperature and pressure range of 50-150 °C and 0-18 bar, respectively. The results showed that the adsorption isotherms of these gases in H-ZSM-5 can be well fitted by Langmuir-type adsorption isotherms. Furthermore, the determined adsorption parameters, i.e., adsorption capacities, adsorption enthalpies, and adsorption entropies, compare well to literature data. In this work, the results for CO2 are shown as an example.

Hierarchy concepts: classification and preparation strategies for zeolite containing materials with hierarchical porosity.

'Hierarchy' is a property which can be attributed to a manifold of different immaterial systems, such as ideas, items and organisations or material ones like biological systems within living organisms or artificial, man-made constructions. The property 'hierarchy' is mainly characterised by a certain ordering of individual elements relative to each other, often in combination with a certain degree of branching. Especially mass-flow related systems in the natural environment feature special hierarchically branched patterns. This review is a survey into the world of hierarchical systems with special focus on hierarchically porous zeolite materials. A classification of hierarchical porosity is proposed based on the flow distribution pattern within the respective pore systems. In addition, this review might serve as a toolbox providing several synthetic and post-synthetic strategies to prepare zeolitic or zeolite containing material with tailored hierarchical porosity. Very often, such strategies with their underlying principles were developed for improving the performance of the final materials in different technical applications like adsorptive or catalytic processes. In the present review, besides on the hierarchically porous all-zeolite material, special focus is laid on the preparation of zeolitic composite materials with hierarchical porosity capable to face the demands of industrial application.

A feasible way to remove the heat during adsorptive methane storage.

Methane originating from biogas or natural gas is an attractive and environmentally friendly alternative to gasoline. Adsorption is seen as promising storage technology, but the heat released limits fast filling of these systems. Here a lab scale adsorptive methane storage tank, capable to study the temperature increase during fast filling, was realized. A variation of the filling time from 1 h to 31 s, showed a decrease of the storage capacity of 14% and temperature increase of 39.6 °C. The experimental data could be described in good accordance with a finite element simulation solving the transient mass, energy, and impulse balance. The simulation was further used to extrapolate temperature development in real sized car tanks and for different heat pipe scenarios, resulting in temperature rises of approximately 110 °C. It could be clearly shown, that with heat conductivity as solei mechanism the heat cannot be removed in acceptable time. By adding an outlet to the tank a feed flow cooling with methane as heat carrier was realized. This setup was proofed in simulation and lab scale experiments to be a promising technique for fast adsorbent cooling and can be crucial to leverage the full potential of adsorptive methane gas storage.