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Critical Role of Dynamic Flexibility in Ge‐Containing Zeolites: Impact on Diffusion
Author(s) -
GutiérrezSevillano Juan José,
Calero Sofía,
Hamad Said,
GrauCrespo Ricardo,
Rey Fernando,
Valencia Susana,
Palomino Miguel,
Balestra Salvador R. G.,
RuizSalvador A. Rabdel
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600983
Subject(s) - flexibility (engineering) , diffusion , rationalization (economics) , molecular dynamics , germanate , germanium , chemical physics , materials science , metastability , nanotechnology , chemistry , computational chemistry , thermodynamics , silicon , physics , organic chemistry , mathematics , optoelectronics , economics , statistics , microeconomics , doping
Incorporation of germanium in zeolites is well known to confer static flexibility to their framework, by stabilizing the formation of small rings. In this work, we show that the flexibility associated to Ge atoms in zeolites goes beyond this static effect, manifesting also a clear dynamic nature, in the sense that it leads to enhanced molecular diffusion. Our study combines experimental and theoretical methods providing evidence for this effect, which has not been described previously, as well as a rationalization for it, based on atomistic grounds. We have used both pure‐silica and silico‐germanate ITQ‐29 (LTA topology) zeolites as a case study. Based on our simulations, we identify the flexibility associated to the pore breathing‐like behavior induced by the Ge atoms, as the key factor leading to the enhanced diffusion observed experimentally in Ge‐containing zeolites.