A structural analysis of zeolite-templated carbons

Abstract

Zeolite-templated carbons (ZTCs) are a distinct class of porous framework materials comprised of a three-dimensional pore network contained between atomically thin, polycyclic hydrocarbon walls. This class of materials arose from the goal to develop carbon- based frameworks with ordered, homogeneous microporosity (see Chapter 1), as opposed to activated carbons where the pore network is random. It has more recently been suggested that zeolite-templating may be a viable synthetic route to carbon schwarzites, an elusive class of theoretical materials, which follow triply periodic minimal surfaces and are predicted to have many fundamentally interesting properties. Herein we show that while experimentally synthesized ZTCs (see Chapters 2 and 3) are too amorphous to be considered schwarzites, understanding the current structural features of ZTCs may be the key to finally isolating a schwarzite via zeolite-templating. The experimentally relevant open- blade model developed in our work predicts paramagnetism of ZTC materials (see Chapter 5); superconducting quantum interference device measurements on archetypical ZTC materials confirms this prediction, highlighting the unique nature of spin polarization in porous carbon materials. While the current ZTC structure resembles an open-blade, generating a closed- tube schwarzite-like ZTC variant may be accessible by tuning the catalytic activity of the zeolite template pore walls. In Chapter 6, alkali metal exchange is explored as a route to strengthen cation-? interactions between the growing ZTC framework and zeolite template in an attempt to achieve a more schwarzite-like ZTC. LiY-templated ZTCs show beginning signs of conversion to a closed-tube structure. Lastly, recent benchmark computational studies suggest that nitrogen-doping of open-blade porous carbon surfaces has a significant, beneficial effect on the binding energy toward methane: a strengthening by up to 3 kJ mol -1 over pure carbon. The work presented in Chapter 7 identifies optimal conditions to achieve nitrogen-doped ZTCs with N-contents ranging from 0-9 at%. Therein, we show that indeed high-pressure (100 bar) methane adsorption characterization of nitrogen-doped ZTCs exhibit an increased methane binding energy of 1.3 kJ mol -1, validating the theoretical predictions.