No abstract

Generating pores in graphene by decoupled nucleation and expansion is desired to achieve a fine control over the porosity, and is desired to advance several applications. Herein, epoxidation is introduced, which is the formation of nanosized epoxy clusters on the graphitic lattice as nucleation sites without forming pores. In situ gasification of clusters inside a transmission electron microscope shows that pores are generated precisely at the site of the clusters by surpassing an energy barrier of 1.3 eV. Binding energy predictions using ab initio calculations combined with the cluster nucleation theory reveal the structure of the epoxy clusters and indicate that the critical cluster is an epoxy dimer. Finally, it is shown that the cluster gasification can be manipulated to form Å‐scale pores which then effectively sieve gas molecules based on their size. This decoupled cluster nucleation and pore formation will likely pave the way for an independent control of pore size and density.

Nanoporous single-layer graphene is promising as an ideal membrane because of its extreme thinness, chemical resistance, and mechanical strength, provided that selective nanopores are successfully incorporated. However, screening and understanding the transport characteristics of the large number of possible pores in graphene are limited by the high computational requirements of molecular dynamics (MD) simulations and the difficulty in experimentally characterizing pores of known structures. MD simulations cannot readily simulate the large number of pores that are encountered in actual membranes to predict transport, and given the huge variety of possible pores, it is hard to narrow down which pores to simulate. Here, we report alternative routes to rapidly screen molecules and nanopores with negligible computational requirement to shortlist selective nanopore candidates. Through the 3D representation and visualization of the pores’ and molecules’ atoms with their van der Waals radii using open-source software, we could identify suitable C-passivated nanopores for both gas- and liquid-phase separation while accounting for the pore and molecule shapes. The method was validated by simulations reported in the literature and was applied to study the mass transport behavior across a given distribution of nanopores. We also designed a second method that accounts for Lennard-Jones and electrostatic interactions between atoms to screen selective non-C-passivated nanopores for gas separations. Overall, these visualization methods can reduce the computational requirements for pore screening and speed up selective pore identification for subsequent detailed MD simulations and guide the experimental design and interpretation of transport measurements in nanoporous atomically thin membranes.

No abstract