Metal-Organic Frameworks in Adsorption-Driven Heat Pumps: The Potential of Alcohols as Working Fluids.

A large fraction of global energy is consumed for heating and cooling. Adsorption-driven heat pumps and chillers could be employed to reduce this consumption. MOFs are often considered to be ideal adsorbents for heat pumps and chillers. While most published works to date on this topic have focused on the use of water as a working fluid, the instability of many MOFs to water and the fact that water cannot be used at subzero temperatures pose certain drawbacks. The potential of using alcohol-MOF pairs in adsorption-driven heat pumps and chillers is investigated. To this end, 18 different selected MOF structures in combination with either methanol or ethanol as a working fluid are considered, and their potential is assessed on the basis of adsorption measurements and thermodynamic efficiencies. If alcohols are used instead of water, then (1) adsorption occurs at lower relative pressures for methanol and even lower pressure for ethanol, (2) larger pores can be utilized efficiently, as hysteresis is absent for pores smaller than 3.4 nm (2 nm for water), (3) larger pore sizes need to be employed to ensure the desired stepwise adsorption, (4) the effect of (polar/apolar) functional groups in the MOF is far less pronounced, (5) the energy released or taken up per cycle is lower, but heat and mass transfer may be enhanced, (6) stability of MOFs seems to be less of an issue, and (7) cryogenic applications (e.g., ice making) become feasible. From a thermodynamic perspective, UiO-67, CAU-3, and ZIF-8 seem to be the most promising MOFs for both methanol and ethanol as working fluids. Although UiO-67 might not be completely stable, both CAU-3 and ZIF-8 have the potential to be applied, especially in subzero-temperature adsorption chillers (AC).