Thin zeolite films prepared through a polymer exfoliation method were used as selective membranes.

The single-layer graphene film, when incorporated with molecular-sized pores, is predicted to be the ultimate membrane. However, the major bottlenecks have been the crack-free transfer of large-area graphene on a porous support, and the incorporation of molecular-sized nanopores. Herein, we report a nanoporous-carbon-assisted transfer technique, yielding a relatively large area (1 mm²), crack-free, suspended graphene film. Gas-sieving (H₂/CH₄ selectivity up to 25) is observed from the intrinsic defects generated during the chemical-vapor deposition of graphene. Despite the ultralow porosity of 0.025%, an attractive H₂ permeance (up to 4.1 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹) is observed. Finally, we report ozone functionalization-based etching and pore-modification chemistry to etch hydrogen-selective pores, and to shrink the pore-size, improving H₂ permeance (up to 300%) and H₂/CH₄ selectivity (up to 150%). Overall, the scalable transfer, etching, and functionalization methods developed herein are expected to bring nanoporous graphene membranes a step closer to reality.

One of the bottlenecks in realizing the potential of atom-thick graphene membrane for gas sieving is the difficulty in incorporating nanopores in an otherwise impermeable graphene lattice, with an angstrom precision at a high-enough pore density. We realize this design by developing a synergistic, partially decoupled defect nucleation and pore expansion strategy using O₂ plasma and O₃ treatment. A high density (ca. 2.1 × 10¹² cm⁻²) of H₂-sieving pores was achieved while limiting the percentage of CH₄-permeating pores to 13 to 22 parts per million. As a result, a record-high gas mixture separation performance was achieved (H₂ permeance, 1340 to 6045 gas permeation units; H₂/CH₄ separation factor, 15.6 to 25.1; H₂/C₃H₈ separation factor, 38.0 to 57.8). This highly scalable pore etching strategy will accelerate the development of single-layer graphene-based energy-efficient membranes.

Poly(triazine imide) (PTI), a crystalline g-C₃N₄, hosting two-dimensional nanoporous structure with an electron density gap of 0.34 nm, is highly promising for high-temperature hydrogen sieving because of its high chemical and thermal robustness. Currently, layered PTI is synthesized in potentially unsafe vacuum ampules in milligram quantities. Here, we demonstrate a scalable and safe ambient pressure synthesis route leading to several grams of layered PTI platelets in a single batch with 70% yield with respect to the precursor. Solvent exfoliation under anhydrous conditions led to single-layer PTI nanosheets evidenced by the observation of triangular g-C₃N₄ nanopores. Gas permeation studies confirm that PTI nanopores can sieve He and H₂ from larger molecules. Last, high-temperature H₂ sieving from PTI nanosheet–based membranes, prepared by the scalable filter coating technique, is demonstrated with H₂ permeance reaching 1500 gas permeation units, with H₂/CO₂, H₂/N₂, and H₂/CH₄ selectivities reaching 10, 50, and 60, respectively, at 250°C.