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.
Porous hybrid materials and MOF (Metal–Organic-Framework) films represent modern designer materials that exhibit many requirements of a near ideal and tunable future thermoelectric (TE) material. In contrast to traditional semiconducting bulk TE materials, porous hybrid MOF templates can be used to overcome some of the constraints of physics in bulk TE materials. These porous hybrid systems are amenable for simulation and modeling to design novel optimized electron-crystal phonon-glass materials with potentially very high ZT (figure of merit) numbers. Porous MOF and hybrid materials possess an ultra-low thermal conductivity, which can be further modulated by phonon engineering within their complex porous and hierarchical architecture to advance the TE figure of merit (ZT). This Perspective review discusses recent results of MOF TE materials and provides a future outlook and the vision to the search for the next generation TE porous hybrid and MOF materials, which could be part of the green renewable energy revolution with novel materials of sustainably high ZT values.
1 January 2009 in Electrochemical and Solid-State Letters
Highly ordered zirconia and hafnia nanotubes were fabricated by atomic layer deposition (ALD) within the anodic alumina oxide (AAO) template. Scanning electron microscopy and energy-dispersive spectroscopy were used to characterize the morphology and elemental compositions of the different ALD coatings. The diameters of the AAO pores are in the range of with a thickness of . The results indicated that the freestanding nanotubes were uniformly grown through the entire template thickness. The ALD process conformally replicated the AAO template dimensions. The number of ALD cycles controlled the resultant nanotube wall thickness.
Thermoelectrics is a green renewable energy technology which can significantly contribute to power generation due to its potential in generating electricity out of waste heat. The main challenge for the development of thermoelectrics is its low conversion efficiency. One key strategy to improve conversion efficiency is reducing the thermal conductivity of thermoelectric materials. In this paper, the state-of-the-art progresses made in improving thermoelectric materials are reviewed and discussed, focusing on phononic engineering via applying porous templates and ALD deposited nanolaminates structure. The effect of nanolaminates structure and porous templates on Seebeck coefficient, electrical conductivity and thermal conductivity, and hence in figure of merit zT of different types of materials system, including PnCs, lead chalcogenide-based nanostructured films on planar and porous templates, ZnO-based superlattice, and hybrid organic-inorganic superlattices, will be reviewed and discussed.