Robust Carborane-Based Metal-Organic Frameworks for Hexane Separation.

Hexane isomers play a vital role as feedstocks and fuel additives in the petrochemical industry. However, their similar physical and chemical properties lead to significant challenges in the separation process. Traditional thermal separation techniques are energy-intensive and lead to significant carbon footprint penalties. As such, there is a growing demand for the development of less energy-intensive nonthermal separation methods. Adsorption-based separation methods, such as using solid sorbents or membranes, have emerged as promising alternatives to distillation. Here, we report the successful synthesis of two novel metal-organic frameworks (MOFs), NU-2004 and NU-2005, by incorporating a carborane-based three-dimensional (3D) linker and using aluminum and vanadium nodes, respectively. These MOFs exhibit exceptional thermal stability and structural rigidity compared to other MIL-53 analogues, which is further corroborated using synchrotron studies. Furthermore, the inclusion of the quasi-spherical 3D linker in NU-2004 demonstrates significant advancements in the separation of hexane isomers compared to other MIL MOFs containing two-dimensional (2D) and aliphatic 3D linkers.

Mesoporous Metastable CuTe2 Semiconductor.

Binary metastable semiconductor materials offer exciting possibilities in the field of optoelectronics, such as photovoltaics, tunable photosensors, and detectors. However, understanding their properties and translating them into practical applications can sometimes be challenging, owing to their thermodynamic instability. Herein, we report a temperature-controlled crystallization technique involving electrochemical deposition to produce metastable CuTe2 thin films that can reliably function under ambient conditions. A series of in situ heating/cooling cycle tests from room temperature to 200 °C followed by spectral, morphological, and compound analyses (such as ultraviolet-visible light spectroscopy, X-ray diffraction (XRD) analysis, and X-ray photoelectron spectroscopy (XPS)) suggest that the seeding electrodes play a key role in the realization of the metastable phase in CuTe2 films. In particular, CuTe2 films deposited on Al electrodes exhibit superior crystallinity and long-term stability compared with those grown on a Au substrate. The XRD data of thermally annealed CuTe2 thin films deposited on Al show a markedly sharp peak, indicating significantly increased crystal-domain sizes. Our method can be used to achieve the metastable phase of CuTe2 with a bandgap of 1.67 eV and offers outstanding photoresponsivity under different illumination conditions.

Engineering Metal-Organic Frameworks for Selective Separation of Hexane Isomers Using 3-Dimensional Linkers.

Metal-organic frameworks (MOFs) are highly tunable materials with potential for use as porous media in non-thermal adsorption or membrane-based separations. However, many separations target molecules with sub-angstrom differences in size, requiring precise control over the pore size. Herein, we demonstrate that this precise control can be achieved by installing a three-dimensional linker in an MOF with one-dimensional channels. Specifically, we synthesized single crystals and bulk powder of NU-2002, an isostructural framework to MIL-53 with bicyclo[1.1.1]pentane-1,3-dicarboxylic acid as the organic linker component. Using variable-temperature X-ray diffraction studies, we show that increasing linker dimensionality limits structural breathing relative to MIL-53. Furthermore, single-component adsorption isotherms demonstrate the efficacy of this material for separating hexane isomers based on the different sizes and shapes of these isomers.

Mixed donor, phenanthroline photoactive MOFs with favourable CO2 selectivity.

Mixed donor phenanthroline-carboxylate linkers were combined with MnII or ZnII to form photoactive MOFs with large pore apertures. The MOFs display high CO2 adsorption capacities, which consequently causes structural framework flexibility, and align with favorable metrics for selective CO2 capture. The photophysical properties of the MOFs were investigated, with the MnII MOF giving rise to short triplet LMCT lifetimes.

Enhancing Multicomponent Metal-Organic Frameworks for Low Pressure Liquid Organic Hydrogen Carrier Separations.

The resurgence of interest in the hydrogen economy could hinge on the distribution of hydrogen in a safe and efficient manner. Whilst great progress has been made with cryogenic hydrogen storage or liquefied ammonia, liquid organic hydrogen carriers (LOHCs) remain attractive due to their lack of need for cryogenic temperatures or high pressures, most commonly a cycle between methylcyclohexane and toluene. Oxidation of methylcyclohexane to release hydrogen will be more efficient if the equilibrium limitations can be removed by separating the mixture. This report describes a family of six ternary and quaternary multicomponent metal-organic frameworks (MOFs) that contain the three-dimensional cubane-1,4-dicarboxylate (cdc) ligand. Of these MOFs, the most promising is a quaternary MOF (CUB-30), comprising cdc, 4,4'-biphenyldicarboxylate (bpdc) and tritopic truxene linkers. Contrary to conventional wisdom that adsorptive interactions with larger, hydrocarbon guests are dominated by π-π interactions, here we report that contoured aliphatic pore environments can exhibit high selectivity and capacity for LOHC separations at low pressures. This is the first time, to the best of our knowledge, where selective adsorption for cyclohexane over benzene is witnessed, underlining the unique adsorptive behavior afforded by the unconventional cubane moiety.