Aspects of Gas Storage: Confined Geometry Effects on the High-Pressure Adsorption Behavior of Supercritical Fluids.

During the last decades, major progress was made concerning the understanding of subcritical low-pressure adsorption of fluids like nitrogen and argon at their boiling temperatures in nanoporous materials. It was possible to understand how structural properties affect the shape of the adsorption isotherms. However, within the context of gas storage applications, supercritical high-pressure gas adsorption is important. A key feature here is that the experimentally determined surface excess adsorption isotherm may exhibit a characteristic maximum at a certain pressure. For a given temperature and adsorptive/adsorbent system, the surface excess maximum (and the corresponding adsorbed amount) is related to the storage capacity of the adsorbent. However, there is still a lack of understanding of how key textural properties such as surface area and pore size affect details of the shape of supercritical high-pressure adsorption isotherms. To address these open questions, we have performed a systematic experimental study assessing the effect of pore size/structure on the supercritical adsorption isotherms of pure fluids such as C2H4, CO2, and SF6 over a wider range of temperatures and pressures on a series of model materials exhibiting well-defined pore sizes, i.e., ordered micro- and mesoporous materials (e.g., NaY zeolite, KIT-6 silica, and MCM-48 silica). A fundamental result of our experiments is a unique fluid-independent correlation between the pressure of the surface excess maximum pmax (at a given temperature) and the pore size (by taking into account the kinetic diameter of the fluid and the underlying effective attractive fluid-wall interaction). Summarizing, our results suggest important structure-property relationships, allowing one to determine, for given thermodynamic conditions, important information related to the optimal operating conditions for supercritical adsorption applications. The insights may also serve as a basis for optimizing and tailoring the properties of nanoporous adsorbent materials for gas storage applications.

Ultrathin Covalent Organic Framework Anchored on Graphene for Enhanced Organic Pollutant Removal.

Covalent organic frameworks (COFs) are of great potential as adsorbents owing to their tailorable functionalities, low density and high porosity. However, their intrinsically stacked two-dimensional (2D) structure limits the full use of their complete surface for sorption, especially the internal pores. The construction of ultrathin COFs could increase the exposure of active sites to the targeted molecules in a pollutant environment. Herein, an ultrathin COF with a uniform thickness of ca. 2 nm is prepared employing graphene as the surface template. The resulting hybrid aerogel with an ultralow density (7.1 mg cm-3 ) exhibits the ability to remove organic dye molecules of different sizes with high efficiency. The three-dimensional (3D) macroporous structure and well-exposed adsorption sites permit rapid diffusion of solution and efficient adsorption of organic pollutants, thereby, greatly contributing to its enhanced uptake capacity. This work highlights the effect of COF layer thickness on adsorption performance.

A Sulfonated Covalent Organic Framework for Atmospheric Water Harvesting.

We report a sulfonated covalent organic framework (COF) capable of atmospheric water harvesting in arid conditions. The isothermal water uptake profile of the framework was studied, and the network displayed steep water sorption at low relative humidity (RH) in temperatures of up to 45 °C, reaching a water uptake of 0.12 g g-1 at 10 % RH and even 0.08 g g-1 at just 5 % RH, representing some of the most extreme conditions on the planet. We found that the inclusion of sulfonate moieties shifted uptake in the water isotherm profiles to lower RH compared to non-sulfonated equivalents, demonstrating well the benefits of including these hydrophilic sites for water uptake in hot, arid locations. Repeated uptake and desorption cycles were performed on the material without significant detriment to its adsorption performance, demonstrating the potential of the sulfonated COF for real-world implementation.

Low-Temperature controlled synthesis of nanocast mixed metal oxide spinels for enhanced OER activity.

The controlled cation substitution is an effective strategy for optimizing the density of states and enhancing the electrocatalytic activity of transition metal oxide catalysts for water splitting. However, achieving tailored mesoporosity while maintaining elemental homogeneity and phase purity remains a significant challenge, especially when aiming for complex multi-metal oxides. In this study, we utilized a one-step impregnation nanocasting method for synthesizing mesoporous Mn-, Fe-, and Ni-substituted cobalt spinel oxide (Mn0.1Fe0.1Ni0.3Co2.5O4, MFNCO) and demonstrate the benefits of low-temperature calcination within a semi-sealed container at 150-200 °C. The comprehensive discussion of calcination temperature effects on porosity, particle size, surface chemistry and catalytic performance for the alkaline oxygen evolution reaction (OER) highlights the importance of humidity, which was modulated by a pre-drying step. The catalyst calcined at 170 °C exhibited the lowest overpotential (335 mV at 10 mA cm-2), highest current density (433 mA cm-2 at 1.7 V vs. RHE, reversible hydrogen electrode) and further displayed excellent stability over 22 h (at 10 mA cm-2). Furthermore, we successfully adapted this method to utilize cheap, commercially available silica gel as a hard template, yielding comparable OER performance. Our results represent a significant progress in the cost-efficient large-scale preparation of complex multi-metal oxides for catalytic applications.