Crystallite Size Effects on the Heat of Water Intrusion/Extrusion into/from Metal–Organic Frameworks

The wettability of nanoporous materials is a key property for a diverse range of applications. However, the heat generated in this process remains largely unexplored. Herein, the heats of intrusion/extrusion into/from ZIF-8 + water systems of various ZIF-8 crystallite sizes were measured at different temperatures. We found that decreasing crystallite size to the nanoscale resulted in a reduction of the magnitude of the heats of intrusion/extrusion. These results were mirrored in simulations, where the reduction of intrusion heat by reducing the characteristics dependent on crystallite size was comparable to the values obtained experimentally. We related this to the reduction in filling at lower pressures. We recorded the inversion of the sign of the heats of intrusion/extrusion measured at high temperatures. In addition, the heat/work ratio of the intrusion/extrusion processes was dependent on temperature while independent of crystallite size, decoupling the two parameters and making them tunable exogenously.