Influence of confinement on free radical chemistry in layered nanostructures.

The purpose of the present work was to study how chemical reactions and the electronic structure of atoms are affected by confinement at the sub-nanometer scale. To reach this goal, we studied the H atom in talc, a layered clay mineral. Talc is a highly 2D-confining material with the width of its interlayer space close to angstrom. We investigated talc with a particle accelerator-based spectroscopic method that uses elementary particles. This technique generates an exotic atom, muonium (Mu), which can be considered as an isotope of the H atom. Moreover, the technique allows us to probe a single atom (H atom) at any time and explore the effects of the layered clay on a single ion (proton) or atom. The cation/electron recombination happens in two time windows: one faster than a nanosecond and the other one at longer than microseconds. This result suggests that two types of electron transfer processes take place in these clay minerals. Calculations demonstrated that the interlayer space acts as a catalytic surface and is the primary location of cation/electron recombination in talc. Moreover, the studies of the temperature dependence of Mu decay rates, due to the formation of the surrogate of H₂, is suggestive of an "H₂" formation reaction that is thermally activated above 25 K, but governed by quantum diffusion below 25 K. The experimental and computational studies of the hyperfine coupling constant of Mu suggest that it is formed in the interlayer space of talc and that its electronic structure is extremely changed due to confinement. All these results imply that the chemistry could be strongly affected by confinement in the interlayer space of clays. [ABSTRACT FROM AUTHOR]