Molecular Insight into Fluorocarbon Adsorption in Pore Expanded Metal-Organic Framework Analogs.

The rapid growth in the global energy demand for space cooling requires the development of more efficient environmental chillers for which adsorption-based cooling systems can be utilized. Here, in this contribution, we explore sorbents for chiller use via a pore-engineering concept to construct analogs of the 1-dimensional pore metal-organic framework MOF-74 by using elongated organic linkers and stereochemistry control. The prepared pore-engineered MOFs show remarkable equilibrium adsorption of the selected fluorocarbon refrigerant that is translated to a modeled adsorption-based refrigeration cycle. To probe molecular level interactions at the origin of these unique adsorption properties for this series of Ni-MOFs, we combined in situ synchrotron X-ray powder diffraction, neutron powder diffraction, X-ray absorption spectroscopy, calorimetry, Fourier transform infrared techniques, and molecular simulations. Our results reveal the coordination of fluorine (of CH2F in R134a) to the nickel(II) open metal centers at low pressures for each Ni-MOF analog and provide insight into the pore filling mechanism for the full range of the adsorption isotherms. The newly designed Ni-TPM demonstrates exceptional R134a adsorption uptake compared to its parent microporous Ni-MOF-74 due to larger engineered pore size/volume. The application of this adsorption performance toward established chiller conditions yields a working capacity increase for Ni-TPM of about 400% from that of Ni-MOF-74, which combined with kinetics directly correlates to both a higher coefficient of performance and a higher average cooling capacity generated in a modeled chiller.

Increased Thermal Conductivity in Metal-Organic Heat Carrier Nanofluids.

Metal-organic heat carriers (MOHCs) are recently developed nanofluids containing metal-organic framework (MOF) nanoparticles dispersed in various base fluids including refrigerants (R245Fa) and methanol. Here, we report the synthesis and characterization of MOHCs containing nanoMIL-101(Cr) and graphene oxide (GO) in an effort to improve the thermo-physical properties of various base fluids. MOHC/GO nanocomposites showed enhanced surface area, porosity, and nitrogen adsorption compared with the intrinsic nanoMIL-101(Cr) and the properties depended on the amount of GO added. MIL-101(Cr)/GO in methanol exhibited a significant increase in the thermal conductivity (by approximately 50%) relative to that of the intrinsic nanoMIL-101(Cr) in methanol. The thermal conductivity of the base fluid (methanol) was increased by about 20%. The increase in the thermal conductivity of nanoMIL-101(Cr) MOHCs due to GO functionalization is explained using a classical Maxwell model.