Membranes act as selective barriers and play an important role in processes such as cellular compartmentalization and industrial-scale chemical and gas purification. The ideal membrane should be as thin as possible to maximize flux, mechanically robust to prevent fracture, and have well-defined pore sizes to increase selectivity. Graphene is an excellent starting point for developing size-selective membranes because of its atomic thickness, high mechanical strength, relative inertness and impermeability to all standard gases. However, pores that can exclude larger molecules but allow smaller molecules to pass through would have to be introduced into the material. Here, we show that ultraviolet-induced oxidative etching can create pores in micrometre-sized graphene membranes, and the resulting membranes can be used as molecular sieves. A pressurized blister test and mechanical resonance are used to measure the transport of a range of gases (H(2), CO(2), Ar, N(2), CH(4) and SF(6)) through the pores. The experimentally measured leak rate, separation factors and Raman spectrum agree well with models based on effusion through a small number of ångstrom-sized pores.

Graphene and other two-dimensional materials offer a new approach to controlling mass transport at the nanoscale. These materials can sustain nanoscale pores in their rigid lattices and due to their minimum possible material thickness, high mechanical strength and chemical robustness, they could be used to address persistent challenges in membrane separations. Here we discuss theoretical and experimental developments in the emerging field of nanoporous atomically thin membranes, focusing on the fundamental mechanisms of gas- and liquid-phase transport, membrane fabrication techniques and advances towards practical application. We highlight potential functional characteristics of the membranes and discuss applications where they are expected to offer advantages. Finally, we outline the major scientific questions and technological challenges that need to be addressed to bridge the gap from theoretical simulations and proof-of-concept experiments to real-world applications.

Dialysis is a ubiquitous separation process in biochemical processing and biological research. State-of-the-art dialysis membranes comprise a relatively thick polymer layer with tortuous pores, and suffer from low rates of diffusion leading to extremely long process times (often several days) and poor selectivity, especially in the 0-1000 Da molecular weight cut-off range. Here, the fabrication of large-area (cm ) nanoporous atomically thin membranes (NATMs) is reported, by transferring graphene synthesized using scalable chemical vapor deposition (CVD) to polycarbonate track-etched supports. After sealing defects introduced during transfer/handling by interfacial polymerization, a facile oxygen-plasma etch is used to create size-selective pores (≤1 nm) in the CVD graphene. Size-selective separation and desalting of small model molecules (≈200-1355 Da) and proteins (≈14 000 Da) are demonstrated, with ≈1-2 orders of magnitude increase in permeance compared to state-of-the-art commercial membranes. Rapid diffusion and size-selectivity in NATMs offers transformative opportunities in purification of drugs, removal of residual reactants, biochemical analytics, medical diagnostics, therapeutics, and nano-bio separations.

We harnessed the hygroscopic and biofluorescent behaviors of microbial cells to design sweat-responsive biohybrid wearables.

Two-dimensional materials such as graphene offer fundamentally transformative opportunities in membrane separations and as impermeable barriers, but the lack of facile methods to assess and control its 'impermeability' critically limits progress. Here we show that a simple etch of the growth catalyst (Cu) through defects in monolayer graphene synthesized by chemical vapor deposition (CVD) can be used to effectively assess graphene quality for membrane/barrier applications. Using feedback from the method to tune synthesis, we realize graphene with nearly no nanometer-scale defects as assessed by diffusion measurements, in contrast to commercially available graphene that is largely optimized for electronic applications. Interestingly, we observe clear evidence of leakage through larger defects associated with wrinkles in graphene, which are selectively sealed to realize centimeter-scale atomically thin barriers exhibiting <2% mass transport compared to the graphene support. Our work provides a facile method to assess and control the 'impermeability' of graphene and shows that future work should be directed towards the control of leakage associated with wrinkles.