title: The assessment of pore connectivity in hierarchical zeolites using positron annihilation lifetime spectroscopy: instrumental and morphological aspects.
abstract: Recent studies demonstrated the power of positron annihilation lifetime spectroscopy (PALS) to characterise the connectivity and corresponding effectiveness of hierarchical pore networks in zeolites. This was based on the fractional escape of ortho-positronium (Ps), formed within the micropore framework, to vacuum. To further develop this technique, here we assess the impact of the positron implantation energy and of the zeolite crystal size and the particle morphology. Conventional measurements using fast positrons and beam measurements applying moderated positrons both readily distinguish purely microporous ZSM-5 zeolites comprised of single crystals or crystal aggregates. Unlike beam measurements, however, conventional measurements fail to discriminate model hierarchical zeolites with open or constricted mesopore architectures. Several steps are taken to rationalise these observations. The dominant contribution of Ps diffusion to the PALS response is confirmed by capping the external surface of the zeolite crystals with tetraethylorthosilicate, which greatly enhances the sensitivity to the micropore network. A one-dimensional model is constructed to predict the out-diffusion of Ps from a zeolite crystal, which is validated experimentally by comparing coffin-shaped single crystals of varying size. Calculation of the trends expected on the application of fast or moderated positrons indicates that the distinctions in the initial distribution of Ps at the crystal level cannot explain the limited sensitivity of the former to the mesopore architecture. Instead, we propose that the greater penetration of fast positrons within the sample increases the probability of Ps re-entry from intercrystalline voids into mesopores connected with the external surface of zeolite crystals, thereby reducing their fractional escape.
authors.affiliation: Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1, CH-8093, Switzerland. sharon.mitchell@chem.ethz.ch.
authors.forename: Asier
authors.initials: A
authors.lastname: Zubiaga
authors.affiliation: Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1, CH-8093, Switzerland. sharon.mitchell@chem.ethz.ch.
authors.forename: Robbie
authors.initials: R
authors.lastname: Warringham
authors.affiliation: Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1, CH-8093, Switzerland. sharon.mitchell@chem.ethz.ch.
authors.forename: Marilyne
authors.initials: M
authors.lastname: Boltz
authors.affiliation: Institute for Particle Physics, Department of Physics, ETH Zürich, Otto-Stern-Weg 5, CH 8093, Switzerland. crivelli@phys.ethz.ch.
authors.forename: David
authors.initials: D
authors.lastname: Cooke
authors.affiliation: Institute for Particle Physics, Department of Physics, ETH Zürich, Otto-Stern-Weg 5, CH 8093, Switzerland. crivelli@phys.ethz.ch.
authors.forename: Paolo
authors.initials: P
authors.lastname: Crivelli
authors.affiliation: Department of Physics, University of Michigan, Ann Arbor, Michigan 48109-1040, USA. gidley@umich.edu.
authors.forename: David
authors.initials: D
authors.lastname: Gidley
authors.affiliation: Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1, CH-8093, Switzerland. sharon.mitchell@chem.ethz.ch.
authors.forename: Javier
authors.initials: J
authors.lastname: Pérez-Ramírez
authors.affiliation: Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1, CH-8093, Switzerland. sharon.mitchell@chem.ethz.ch.
authors.forename: Sharon
authors.initials: S
authors.lastname: Mitchell