Mild-Temperature Supercritical Water Confined in Hydrophobic Metal- Organic Frameworks

S Merchiori and A Le Donne and JD Littlefair and AR Lowe and JJ Yu and XD Wu and M Li and D Li and M Geppert-Rybczynska and L Scheller and BA Trump and AA Yakovenko and P Zajdel and M Chorazewski and Y Grosu and S Meloni, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 146, 13236-13246 (2024).

DOI: 10.1021/jacs.4c01226

Fluids under extreme confinement show characteristics significantly different from those of their bulk counterpart. This work focuses on water confined within the complex cavities of highly hydrophobic metal- organic frameworks (MOFs) at high pressures. A combination of high- pressure intrusion-extrusion experiments with molecular dynamic simulations and synchrotron data reveals that supercritical transition for MOF-confined water takes place at a much lower temperature than in bulk water, similar to 250 K below the reference values. This large shifting of the critical temperature (T-c) is attributed to the very large density of confined water vapor in the peculiar geometry and chemistry of the cavities of Cu(2)tebpz (tebpz = 3,3 ',5,5 '-tetraethyl-4,4 '-bipyrazolate) hydrophobic MOF. This is the first time the shift of T-c is investigated for water confined within highly hydrophobic nanoporous materials, which explains why such a large reduction of the critical temperature was never reported before, neither experimentally nor computationally.

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