Kinetic Control of Angstrom-Scale Porosity in 2D Lattices for Direct Scalable Synthesis of Atomically Thin Proton...

Angstrom-scale pores introduced into atomically thin 2D materials offer transformative advances for proton exchange membranes in several energy applications. Here, we show that facile kinetic control of scalable chemical vapor deposition (CVD) can allow for direct formation of angstrom-scale proton-selective pores in monolayer graphene with significant hindrance to even small, hydrated ions (K⁺ diameter ∼6.6 Å) and gas molecules (H₂ kinetic diameter ∼2.9 Å). We demonstrate centimeter-scale Nafion|Graphene|Nafion membranes with proton conductance ∼3.3-3.8 S cm^-2 (graphene ∼12.7-24.6 S cm^-2) and H⁺/K⁺ selectivity ∼6.2-44.2 with liquid electrolytes. The same membranes show proton conductance ∼4.6-4.8 S cm^-2 (graphene ∼39.9-57.5 S cm^-2) and extremely low H₂ crossover ∼1.7 × 10^-1 - 2.2 × 10^-1 mA cm^-2 (∼0.4 V, ∼25 °C) with H₂ gas feed. We rationalize our findings via a resistance-based transport model and introduce a stacking approach that leverages combinatorial effects of interdefect distance and interlayer transport to allow for Nafion|Graphene|Graphene|Nafion membranes with H⁺/K⁺ selectivity ∼86.1 (at 1 M) and record low H₂ crossover current density ∼2.5 × 10^-2 mA cm^-2, up to ∼90% lower than state-of-the-art ionomer Nafion membranes ∼2.7 × 10^-1 mA cm^-2 under identical conditions, while still maintaining proton conductance ∼4.2 S cm^-2 (graphene stack ∼20.8 S cm^-2) comparable to that for Nafion of ∼5.2 S cm^-2. Our experimental insights enable functional atomically thin high flux proton exchange membranes with minimal crossover.