Gas adsorption and framework flexibility of CALF-20 explored via experiments and simulations.

In 2021, Svante, in collaboration with BASF, reported successful scale up of CALF-20 production, a stable MOF with high capacity for post-combustion CO2 capture which exhibits remarkable stability towards water. CALF-20's success story in the MOF commercialisation space provides new thinking about appropriate structural and adsorptive metrics important for CO2 capture. Here, we combine atomistic-level simulations with experiments to study adsorptive properties of CALF-20 and shed light on its flexible crystal structure. We compare measured and predicted CO2 and water adsorption isotherms and explain the role of water-framework interactions and hydrogen bonding networks in CALF-20's hydrophobic behaviour. Furthermore, regular and enhanced sampling molecular dynamics simulations are performed with both density-functional theory (DFT) and machine learning potentials (MLPs) trained to DFT energies and forces. From these simulations, the effects of adsorption-induced flexibility in CALF-20 are uncovered. We envisage this work would encourage development of other MOF materials useful for CO2 capture applications in humid conditions.

Designed Synthesis of Mesoporous Solid-Supported Lewis Acid-Base Pairs and Their CO2 Adsorption Behaviors.

Conventional amines and phosphines, such as diethylenetriamine, diphenylpropylphosphine, triethylamine, and tetramethylpiperidine, were grafted or impregnated on the surface of metalated SBA-15 materials, such as Ti-, Al-, and Zr-SBA-15, to generate air-stable solid-supported Lewis acid-base pairs. The Lewis acidity of the metalated materials before and after the introduction of Lewis bases was verified by means of pyridine adsorption-Fourier transform infrared spectroscopy. Detailed characterization of the materials was achieved by solid-state 13C and 31P MAS NMR spectroscopy, low-temperature N2 physisorption, X-ray photoelectron spectroscopy, and energy-dispersive X-ray mapping analyses. Study of their potential interactions with CO2 was performed using CO2 adsorption isotherm experiments, which provided new insights into their applicability as solid CO2 adsorbents. A correlation between solid-supported Lewis acid-base pair strength and the resulting affinity to CO2 is discussed based on the calculation of isosteric enthalpy of adsorption.

Synthesis of Engineered Zeolitic Materials: From Classical Zeolites to Hierarchical Core-Shell Materials.

The term "engineered zeolitic materials" refers to a class of materials with a rationally designed pore system and active-sites distribution. They are primarily made of crystalline microporous zeolites as the main building blocks, which can be accompanied by other secondary components to form composite materials. These materials are of potential importance in many industrial fields like catalysis or selective adsorption. Herein, critical aspects related to the synthesis and modification of such materials are discussed. The first section provides a short introduction on classical zeolite structures and properties, and their conventional synthesis methods. Then, the motivating rationale behind the growing demand for structural alteration of these zeolitic materials is discussed, with an emphasis on the ongoing struggles regarding mass-transfer issues. The state-of-the-art techniques that are currently available for overcoming these hurdles are reviewed. Following this, the focus is set on core-shell composites as one of the promising pathways toward the creation of a new generation of highly versatile and efficient engineered zeolitic substances. The synthesis approaches developed thus far to make zeolitic core-shell materials and their analogues, yolk-shell, and hollow materials, are also examined and summarized. Finally, the last section concisely reviews the performance of novel core-shell, yolk-shell, and hollow zeolitic materials for some important industrial applications.

Selective Separation and Preconcentration of Scandium with Mesoporous Silica.

Separation and preconcentration of scandium (Sc) were successfully achieved using a mesoporous silica support that showed good selectivity for this element. Unmodified mesoporous silica materials were used as an extracting medium in a solid-liquid extraction (SLE) process. Selectivity, extraction capacity, kinetics of extraction, and reusability under acidic conditions were investigated. The results demonstrate the potential of unmodified mesoporous silica materials for the selective separation and preconcentration of Sc. As no chelating ligand was grafted on the silica surface, which is often the case for most solid-phase extraction media for metal-ion separation, the experimental data allow us to hypothesize that the accessible silanols on the material surface are responsible for the selective Sc extraction. This interesting feature would drastically decrease the cost of solid-liquid extraction systems by using unmodified mesoporous silica materials. Moreover, a leachate solution obtained from a real rare-earth element ore was used to determine the performances of the proposed materials in a packed column configuration. The maximum Sc adsorption on the silica material surfaces is moderate (1 mg/g), but it is balanced by a great concentration factor (more than 100 times). The extraction performances are potentially promising, both in terms of selectivity and preconcentration, under the acidic conditions tested.

Zeolitic Core@Shell Adsorbents for the Selective Removal of Free Glycerol from Crude Biodiesel.

Selective adsorption of free glycerol from crude biodiesel was investigated by using mesoporous silica spheres coated with a thin shell of microporous silicalite-1. A polycrystalline silicalite-1 shell was formed upon first covering the external surfaces of various core templates with discrete silicalite-1 nanocrystals, and this was followed by short hydrothermal treatment to ensure shell uniformity. Batch glycerol adsorption experiments were conducted to evaluate the ability of the sorbents to remove free glycerol selectively from crude biodiesel mixtures at various temperatures, also in comparison to that of conventional sorbents, for example, bare mesoporous silica gel spheres and zeolites. The silicalite-1 shell provided a microporous membrane that hindered the diffusion of fatty acid methyl esters into the mesopores of the composite sorbent, whereas the large pore volume of the mesoporous core enabled multilayer glycerol adsorption; this ultimately substantially enhanced the performance in terms of purification yield and adsorption capacity.