Approximating Standard Formation Enthalpies of Porous Metal–Organic Frameworks: Extending a Gas-Phase Approach to Porous Solids

Abstract

The unique properties of porous metal–organic frameworks (MOFs) make them amenable to simple estimation of their standard formation enthalpies(ΔHf◦) using a modification to Benson group increment theory (BGIT); this approach fills a void in the literature because extracting such data from first-principles calculations is generally not computationally feasible. The method is illustrated for MOFs based on both the basic Zn carboxylate and Cu paddlewheel secondary building units, with approaches outlined for further extension to additional MOF classes. Simple access to ΔHf◦(MOF) values informs stability relationships between dense and porous phases and is critical for applications involving energetic MOF composites.