Observation of reduced thermal conductivity in a metal-organic framework due to the presence of adsorbates

Whether the presence of adsorbates increases or decreases thermal conductivity in metal-organic frameworks (MOFs) has been an open question. Here we report observations of thermal transport in the metal-organic framework HKUST-1 in the presence of various liquid adsorbates: water, methanol, and ethanol. Experimental thermoreflectance measurements were performed on single crystals and thin films, and theoretical predictions were made using molecular dynamics simulations. We find that the thermal conductivity of HKUST-1 decreases by 40 – 80% depending on the adsorbate, a result that cannot be explained by effective medium approximations. Our findings demonstrate that adsorbates introduce additional phonon scattering in HKUST-1, which particularly shortens the lifetimes of low-frequency phonon modes. As a result, the system thermal conductivity is lowered to a greater extent than the increase expected by the creation of additional heat transfer channels. Finally, we show that thermal diffusivity is even more greatly reduced than thermal conductivity by adsorption

Benign by Design: Green and Scalable Synthesis of Zirconium UiO-Metal–Organic Frameworks by Water-Assisted Mechanochemistry

We present a solvent-free, green, and rapid mechanochemical route for the synthesis of a series of zirconium metal–organic frameworks (MOFs) composed of Zr6 cluster nodes, UiO-66, UiO-66-NH2, MOF-801, and MOF-804, both on a laboratory scale and by scalable and flow mechanochemical processing. The methodology, based on the use of a nonconventional zirconium dodecanuclear acetate cluster and a minute amount of water as an additive, affords high-quality MOFs in less than 1 h of milling, with minimal requirements for workup processing and eliminating the need for conventional hazardous solvents, such as dimethylformamide. Moreover, the use of a dodecanuclear zirconium acetate precursor circumvents the need for modulators resulting in acetic acid as the only byproduct of the reaction, which does not harm these acid-resistant materials. The porosity, thermal and chemical stability, as well as catalytic activity of mechanochemically prepared Zr-based MOFs are similar to those of solvothermally synthesized counterparts. Finally, the synthesis is readily applicable on a 10 g scale by using a planetary mill, and is also performed by solid-state flow synthesis using twin-screw extrusion (TSE), affording more than 100 g of catalytically active UiO-66-NH2 material in a continuous process at a rate of 1.4 kg/h

How reproducible are surface areas calculated from the BET equation?

Porosity and surface area analysis play a prominent role in modern materials science. At the heart of this sits the Brunauer-Emmett-Teller (BET) theory, which has been a remarkably successful contribution to the field of materials science. The BET method was developed in the 1930s for open surfaces but is now the most widely used metric for the estimation of surface areas of micro- and mesoporous materials. Despite its widespread use, the calculation of BET surface areas causes a spread in reported areas, resulting in reproducibility problems in both academia and industry. To prove this, for this analysis, 18 already-measured raw adsorption isotherms were provided to sixty-one labs, who were asked to calculate the corresponding BET areas. This round-robin exercise resulted in a wide range of values. Here, the reproducibility of BET area determination from identical isotherms is demonstrated to be a largely ignored issue, raising critical concerns over the reliability of reported BET areas. To solve this major issue, a new computational approach to accurately and systematically determine the BET area of nanoporous materials is developed. The software, called "BET surface identification" (BETSI), expands on the well-known Rouquerol criteria and makes an unambiguous BET area assignment possible

Current trend in synthesis, Post-Synthetic modifications and biological applications of Nanometal-Organic frameworks (NMOFs)

Since the early reports of MOFs and their interesting properties, research involving these materials has grown wide in scope and applications. Various synthetic approaches have ensued in view of obtaining materials with optimised properties, the extensive scope of application spanning from energy, gas sorption, catalysis biological applications has meant exponentially evolved over the years. The far‐reaching synthetic and PSM approaches and porosity control possibilities have continued to serve as a motivation for research on these materials. With respect to the biological applications, MOFs have shown promise as good candidates in applications involving drug delivery, BioMOFs, sensing, imaging amongst others. Despite being a while away from successful entry into the market, observed results in sensing, drug delivery, and imaging put these materials on the spot light as candidates poised to usher in a revolution in biology. In this regard, this review article focuses current approaches in synthesis, post functionalization and biological applications of these materials with particular attention on drug delivery, imaging, sensing and BioMOFs

Performance prediction for non-adiabatic capillary tube suction line heat exchanger: an artificial neural network approach

This study presents an application of the artificial neural network (ANN) model using the back propagation (BP) learning algorithm to predict the performance (suction line outlet temperature and mass flow rate) of a non-adiabatic capillary tube suction line heat exchanger, basically used as a throttling device in small household refrigeration systems. Comparative studies were made by using an ANN model, experimental results and correlations to predict the performance. These studies showed that the proposed approach could successfully be used for performance prediction for the exchanger. (C) 2004 Elsevier Ltd. All rights reserved

Effects on residual stresses of annealing parameters in high-temperature ZrO2 insulation coatings on Ag/Bi-2212 superconducting tapes using finite element method

In the present work, we focus on effects of residual stresses of annealing parameters and fracture behavior in high-temperature ZrO2 insulation coatings on Ag/Bi-2212 superconducting tapes using the finite element method. High-temperature ZrO2-based insulation ceramic coatings were produced on Ag and Ag/AgMg sheathed Bi-2212 superconducting tapes by the reel-to-reel sol-gel technique for magnet technology. The samples produced were characterized using scanning electron microscopy (SEM). These coatings are exposed to thermal loading under several annealing conditions. The residual stresses in 8-mum-thick coatings, as well as changes during thermal cycling, were simulated by finite element analysis (FEA). It was found that the shear stress values of ZrO2 coatings in the interface were very low, and the maximum shear stress was 47 Pa for 8-mum-thick coatings. It was determined that the highest fracture intensity was 1.09 x 10(-4) MN m(-3/2), and the fracture intensity decreased as a function of distance from the initial crack. (C) 2002 Elsevier Science Ltd. All rights reserved