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

Autor: Merchiori S; Department of Chemical, Pharmaceutical and Agricultural Sciences, University of Ferrara, 44121 Ferrara, Italy., Le Donne A; Department of Chemical, Pharmaceutical and Agricultural Sciences, University of Ferrara, 44121 Ferrara, Italy., Littlefair JD; Department of Chemical, Pharmaceutical and Agricultural Sciences, University of Ferrara, 44121 Ferrara, Italy., Lowe AR; Institute of Chemistry, University of Silesia, Szkolna 9, 40-006 Katowice, Poland., Yu JJ; College of Chemistry and Chemical Engineering, and Chemistry and Chemical Engineering Guangdong Laboratory, Shantou University, Guangdong 515063, China., Wu XD; College of Chemistry and Chemical Engineering, and Chemistry and Chemical Engineering Guangdong Laboratory, Shantou University, Guangdong 515063, China., Li M; College of Chemistry and Chemical Engineering, and Chemistry and Chemical Engineering Guangdong Laboratory, Shantou University, Guangdong 515063, China., Li D; College of Chemistry and Materials Science, Jinan University, Guangzhou 510632, China., Geppert-Rybczyńska M; Institute of Chemistry, University of Silesia, Szkolna 9, 40-006 Katowice, Poland., Scheller L; Institute of Physics, University of Silesia, 41-500 Chorzów, Poland., Trump BA; NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, United States., Yakovenko AA; X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, United States., Zajdel P; Institute of Physics, University of Silesia, 41-500 Chorzów, Poland., Chorążewski M; Institute of Chemistry, University of Silesia, Szkolna 9, 40-006 Katowice, Poland., Grosu Y; Institute of Chemistry, University of Silesia, Szkolna 9, 40-006 Katowice, Poland.; Centre for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), 01510 Vitoria-Gasteiz, Spain., Meloni S; Department of Chemical, Pharmaceutical and Agricultural Sciences, University of Ferrara, 44121 Ferrara, Italy.
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2024 May 15; Vol. 146 (19), pp. 13236-13246. Date of Electronic Publication: 2024 May 03.
DOI: 10.1021/jacs.4c01226
Abstrakt: 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, ∼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.
Databáze: MEDLINE