Effect of Crystallite Size on the Flexibility and Negative Compressibility of Hydrophobic Metal–Organic Frameworks

Johnson, Liam J. W.; Mirani, Diego; Le Donne, Andrea; Bartolomé, Luis; Amayuelas, Eder; López, Gabriel A.; Grancini, Giulia; Carter, Marcus; Yakovenko, Andrey A.; Trump, Benjamin A.; Meloni, Simone; Zajdel, Paweł; Grosu, Yaroslav

doi:10.1021/acs.nanolett.3c02431

Cited by 1 publication

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“…Once established that the change of the specific heat capacity between intruded and extruded states is responsible for the trend of heat of intrusion on the temperature, the authors focused on the possible origin of the sign and absolute value of Δ c p . From previous simulations and experiments, it is estimated that the density of water confined within ZIF-8 cavities is approximated to be 0.7 kg·dm –3 , which is much lower than the value of the bulk liquid. ,, It is also noticed that the specific heat of bulk liquid water decreases with increasing density . Thus, the authors expect that the reduction of the density upon intrusion, from the bulk to the liquid-like confined value, is associated with an increase of heat capacity of bulk water (a positive Δ c p ), which is consistent with simulation results.…”

Section: Modeling Temperature Dependencesupporting

confidence: 79%

Exploring the Heat of Water Intrusion into a Metal–Organic Framework by Experiment and Simulation

Lowe,

Ślęczkowski,

Arkan

et al. 2024

ACS Appl. Mater. Interfaces

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Wetting of a solid by a liquid is relevant for a broad range of natural and technological processes. This process is complex and involves the generation of heat, which is still poorly understood especially in nanoconfined systems. In this article, scanning transitiometry was used to measure and evaluate the pressure-driven heat of intrusion of water into solid ZIF-8 powder within the temperature range of 278.15–343.15 K. The conditions examined included the presence and absence of atmospheric gases, basic pH conditions, solid sample origins, and temperature. Simultaneously with these experiments, molecular dynamics simulations were conducted to elucidate the changing behavior of water as it enters into ZIF-8. The results are rationalized within a temperature-dependent thermodynamic cycle. This cycle describes the temperature-dependent process of ZIF-8 filling, heating, emptying, and cooling with respect to the change of internal energy of the cycle from the calculated change in the specific heat capacity of the system. At 298 K the experimental heat of intrusion per gram of ZIF-8 was found to be −10.8 ± 0.8 J·g–1. It increased by 19.2 J·g–1 with rising temperature to 343 K which is in a reasonable match with molecular dynamic simulations that predicted 16.1 J·g–1 rise. From these combined experiments, the role of confined water in heat of intrusion of ZIF-8 is further clarified.

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