TY - JOUR
T1 - A Nanocavitation Approach to Understanding Water Capture, Water Release, and Framework Physical Stability in Hierarchically Porous MOFs
AU - Liu, Jian
AU - Prelesnik, Jesse L.
AU - Patel, Roshan
AU - Kramar, Boris V.
AU - Wang, Rui
AU - Malliakas, Christos D.
AU - Chen, Lin X.
AU - Siepmann, J. Ilja
AU - Hupp, Joseph T.
N1 - Publisher Copyright:
© 2023 American Chemical Society
PY - 2023/12/27
Y1 - 2023/12/27
N2 - Chemically stable metal-organic frameworks (MOFs) featuring interconnected hierarchical pores have proven to be promising for a remarkable variety of applications. Nevertheless, the framework’s susceptibility to capillary-force-induced pore collapse, especially during water evacuation, has often limited practical applications. Methodologies capable of predicting the relative magnitudes of these forces as functions of the pore size, chemical composition of the pore walls, and fluid loading would be valuable for resolution of the pore collapse problem. Here, we report that a molecular simulation approach centered on evacuation-induced nanocavitation within fluids occupying MOF pores can yield the desired physical-force information. The computations can spatially pinpoint evacuation elements responsible for collapse and the chemical basis for mitigation of the collapse of modified pores. Experimental isotherms and difference-electron density measurements of the MOF NU-1000 and four chemical variants validate the computational approach and corroborate predictions regarding relative stability, anomalous sequence of pore-filling, and chemical basis for mitigation of destructive forces.
AB - Chemically stable metal-organic frameworks (MOFs) featuring interconnected hierarchical pores have proven to be promising for a remarkable variety of applications. Nevertheless, the framework’s susceptibility to capillary-force-induced pore collapse, especially during water evacuation, has often limited practical applications. Methodologies capable of predicting the relative magnitudes of these forces as functions of the pore size, chemical composition of the pore walls, and fluid loading would be valuable for resolution of the pore collapse problem. Here, we report that a molecular simulation approach centered on evacuation-induced nanocavitation within fluids occupying MOF pores can yield the desired physical-force information. The computations can spatially pinpoint evacuation elements responsible for collapse and the chemical basis for mitigation of the collapse of modified pores. Experimental isotherms and difference-electron density measurements of the MOF NU-1000 and four chemical variants validate the computational approach and corroborate predictions regarding relative stability, anomalous sequence of pore-filling, and chemical basis for mitigation of destructive forces.
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U2 - 10.1021/jacs.3c07624
DO - 10.1021/jacs.3c07624
M3 - Article
C2 - 38085867
AN - SCOPUS:85180115897
SN - 0002-7863
VL - 145
SP - 27975
EP - 27983
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 51
ER -