Selective Photonic Gasification of Strained Oxygen Clusters on Graphene for Tuning Pore Size in the Å Regime

[Image: see text] Controlling the size of single-digit pores, such as those in graphene, with an Å resolution has been challenging due to the limited understanding of pore evolution at the atomic scale. The controlled oxidation of graphene has led to Å-scale pores; however, obtaining a fine control over pore evolution from the pore precursor (i.e., the oxygen cluster) is very attractive. Herein, we introduce a novel “control knob” for gasifying clusters to form pores. We show that the cluster evolves into a core/shell structure composed of an epoxy group surrounding an ether core in a bid to reduce the lattice strain at the cluster core. We then selectively gasified the strained core by exposing it to 3.2 eV of light at room temperature. This allowed for pore formation with improved control compared to thermal gasification. This is because, for the latter, cluster–cluster coalescence via thermally promoted epoxy diffusion cannot be ruled out. Using the oxidation temperature as a control knob, we were able to systematically increase the pore density while maintaining a narrow size distribution. This allowed us to increase H(2) permeance as well as H(2) selectivity. We further show that these pores could differentiate CH(4) from N(2), which is considered to be a challenging separation. Dedicated molecular dynamics simulations and potential of mean force calculations revealed that the free energy barrier for CH(4) translocation through the pores was lower than that for N(2). Overall, this study will inspire research on the controlled manipulation of clusters for improved precision in incorporating Å-scale pores in graphene.