RT Journal Article
T1 Understanding Nanopore Window Distortions in the Reversible Molecular Valve Zeolite RHO
A1 Balestra, Salvador R. G.
A1 Hamad, Said
A1 Ruiz-Salvador, A. Rabdel
A1 Domínguez−García, V.
A1 Merkling, Patrick
A1 Dubbeldam, D.
A1 Calero, Sofía
K1 Zeolite
K1 Molecular valve
K1 Flexibitity
K1 Structural relaxation
K1 Modeling
K1 Phase transition
AB Molecular valves are becoming popular for potential biomedical applications. However, little is known concerning their performance in energy and environmental areas. Zeolite RHO shows unique pore deformations upon changes in hydration, cation siting, cation type, or temperature–pressure conditions. By varying the level of distortion of double eight-rings, it is possible to control the adsorption properties, which confer a molecular valve behavior to this material. We have employed interatomic potentials-based simulations to obtain a detailed atomistic view of the structural distortion mechanisms of zeolite RHO, in contrast with the averaged and space group restricted information provided by diffraction studies. We have modeled four aluminosilicate structures, containing Li+, Na+, K+, Ca2+ cations. The distortions of the three different zeolite rings are coupled, and the six- and eight-membered rings are largely flexible. A large dependence on the polarizing power of the extra-framework cations and with the loading of water has been found for the minimum aperture of the eight-membered rings that control the nanovalve effect. The calculated energy barriers for moving the cations across the eight-membered rings are very high, which explains the experimentally observed slow kinetics of the phase transition as well as the appearance of metastable phases.
PB American Chemical Society
YR 2015
FD 2015-07-14
LK https://hdl.handle.net/10433/20011
UL https://hdl.handle.net/10433/20011
LA en
NO Chem. Mater. 2015, 27, 16, 5657–5667
NO Departamento de Sistemas Físicos, Químicos y Naturales
DS RIO
RD May 9, 2026