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Many properties of the emerging class of metal‐organic frameworks (MOFs) depend crucially on defect concentrations, as in case of other solids. In order to provide reference systems with nearly perfect structure and low defect density, a procedure to grow MOFs epitaxially on cm‐sized Si(111) single crystals is developed. The crystalline metal‐organic thin films are in high registry with the substrate's crystal lattice, as demonstrated by synchrotron‐based grazing incidence X‐ray diffraction (GI‐XRD) experiments. The corresponding reduction of MOF defect density is shown to have striking effects on the properties of these porous frameworks. The most pronounced difference concerns mass transport. An increase in the diffusion coefficient of guest molecules by one order of magnitude relative to the same MOF materials with normal defect densities is observed. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs) have gained substantial attention as promising materials for gas separation membranes due to their exceptional porosity, tailorability, and functionalizability. In this study, we present a novel approach to further enhance the properties of porous polymer membranes emerging from MOFs through crosslinking of the organic linker molecules and subsequent metal-atom removal. To ensure reproducibility of the multi-step synthesis process and high quality of the resulting polymeric membranes, we automated the process and followed a machine learning optimization approach. The high-quality MOF-thin films (SURMOFs) were prepared in a layer-by-layer fashion directly on gold-coated porous alumina substrates. This direct synthesis proved crucial to preserve the structural integrity of the membranes and thus avoiding defect formation caused by a substrate-transfer process, which is usually required when advanced materials are used to fabricate a membrane. The initial SURMOF membrane exhibits moderate gas separation performance, once crosslinked, its gas selectivity could be significantly enhanced although with the compromise of lower gas permeance. Interestingly, once we removed the metal centers and thereby converted the SURMOF into a purely organic polymeric membrane, the membrane gas permeance could be restored almost to its initial condition while preserving the enhanced selectivities. In particular, the resulting polymeric membrane outperforms most commercially available polymer membranes for H2/CO2 gas separation. This research outlines a promising approach to employ MOFs as template in the generation of advanced polymer membranes for various gas and liquid phase separation applications. [ABSTRACT FROM AUTHOR]

Metal-organic frameworks (MOFs), have emerged as ideal class of materials for the identification of structure-property relationships and for the targeted design of multifunctional materials for diverse applications. While the powder form is most common, for the integration of MOFs into devices, typically thin films of surface anchored MOFs (SURMOFs), are required. Although the quality of SURMOFs emerging from layer-by-layer approaches is impressive, previous works revealed that the optimum growth conditions are very different between different types of MOFs and different substrates. Furthermore, the choice of appropriate synthesis conditions (e.g., solvents, modulators, concentrations, immersion times) is crucial for the growth process and needs to be adjusted for different substrates. Machine learning (ML) approaches show great promise for multi-parameter optimization problems such as the above discussed growth conditions for SURMOF on a particular substrate. Here, this work presents an ML-based approach allowing to quickly identify optimized growth conditions for HKUST-I SURMOFs with high crystallinity and uniform orientation. This process can subsequently be used to optimize growth on other types of substrates. In addition, an analysis of the results allows to gain further insights into the factors governing the growth of MOF thin films. [ABSTRACT FROM AUTHOR]

It is often of great importance in engineering to know precisely the properties of a material used with regard to its strength, its plasticity or its brittleness, its elasticity, and some other properties. For this purpose, material samples are tested in a tensile test by clamping the sample with a known starting cross-section in a tensile testing machine and loading it with a tensile force F. The force is then graphically displayed over the length change ΔL caused. This curve is called the force-extension diagram. In this study, a new measurement method enables for the first time, depending on the applied uniaxial stress, an insight at the atomic level into various energy dissipation processes at cement-based materials with the help of infrared spectroscopy. The samples are modified by adding SiO2 particles, which are coated by a polymer (PEG-MDI-DMPA) of different PEG molecular weights. Results show that elongating and breakage of S i − O − S i and C − O bonds play an essential role in the strain energy dissipation. Compared to the pure cement, the modified samples are affected more by elongating and breakage of S i − O − S i , as the admixture can effectively reduce the energy barrier of the hydrolytic reaction. The incorporating of particles into the cement matrix induces new mechanisms for energy dissipation by stretching of O − S i − O bending vibrations. Stretching vibration of the O − H group indicates that part of the energy is dissipated by breakage of hydrogen bonding between the carboxyl group and PEG chains. Besides, a higher value of the ultimate fracture force following an increase in the molecular weight of PEG shows stronger bonding between particles and the cement matrix. As the chain-length of PEG is increased, less energy is absorbed through the other processes (especially at a higher level of strain). Thus, there is a balance between the whole deformation (toughness) and the strength of samples with the increase of the PEG molecular weight. [ABSTRACT FROM AUTHOR]

Understanding the changes that occur in the micro-mechanical properties of semiconductor materials is of utmost importance for the design of new flexible electronic devices, especially to control the properties of newly designed materials. In this work, we present the design, fabrication, and application of a novel tensile-testing device coupled to FTIR measurements that enables in situ atomic investigations of samples under uniaxial tensile load. The device allows for mechanical studies of rectangular samples with dimensions of 30 mm × 10 mm × 0.5 mm. By recording the alternation in dipole moments, the investigation of fracture mechanisms becomes feasible. Our results show that thermally treated SiO 2 on silicon wafers has a higher strain resistance and breaking force than the SiO 2 native oxide. The FTIR spectra of the samples during the unloading step indicate that for the native oxide sample, the fracture happened following the propagation of cracks from the surface into the silicon wafer. On the contrary, for the thermally treated samples, the crack growth starts from the deepest region of the oxide and propagates along the interface due to the change in the interface properties and redistribution of the applied stress. Finally, density functional theory calculations of model surfaces were conducted in order to unravel the differences in optic and electronic properties of the interfaces with and without applied stress., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Despite their huge potential for efficient molecular separation, the fabrication of membranes from metal-organic frameworks (MOFs) remains a major challenge. The powders obtained by the conventional solvothermal MOF syntheses are difficult to process, and as a result the fabrication of well-performing, large-area MOF-based membranes is still awaiting success. The deposition of MOF thin films suited for membrane applications is demonstrated by employing a step-by-step spray method. This method can be scaled up to obtain industrially relevant membrane areas and a continuous process is also possible. The performance of sprayed HKUST-1-based membranes by the separation of a binary H 2 /CO 2 mixture is also demonstrated. Furthermore, this approach enables the control of the MOF film thickness, and thus controlling the permeance and the selectivity of the membrane., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)