Michael S. H. Boutilier

Selective Ionic Transport through Tunable Subnanometer Pores in Single-Layer Graphene Membranes

We report selective ionic transport through controlled, high-density, subnanometer diameter pores in macroscopic single-layer graphene membranes. Isolated, reactive defects were first introduced into the graphene lattice through ion bombardment and subsequently enlarged by oxidative etching into permeable pores with diameters of 0.40 ± 0.24 nm and densities exceeding 10(12) cm(-2), while retaining structural integrity of the graphene. Transport measurements across ion-irradiated graphene membranes subjected to in situ etching revealed that the created pores were cation-selective at short oxidation times, consistent with electrostatic repulsion from negatively charged functional groups terminating the pore edges. At longer oxidation times, the pores allowed transport of salt but prevented the transport of a larger organic molecule, indicative of steric size exclusion. The ability to tune the selectivity of graphene through controlled generation of subnanometer pores addresses a significant challenge in the development of advanced nanoporous graphene membranes for nanofiltration, desalination, gas separation, and other applications.

Selective molecular transport through intrinsic defects in a single layer of CVD graphene.

We report graphene composite membranes with nominal areas more than 25 mm(2) fabricated by transfer of a single layer of CVD graphene onto a porous polycarbonate substrate. A combination of pressure-driven and diffusive transport measurements provides evidence of size-selective transport of molecules through the membrane, which is attributed to the low-frequency occurrence of intrinsic 1-15 nm diameter pores in the CVD graphene. Our results present the first step toward the realization of practical membranes that use graphene as the selective material.

Mechanisms of Molecular Permeation through Nanoporous Graphene Membranes

We present an investigation of molecular permeation of gases through nanoporous graphene membranes via molecular dynamics simulations; four different gases are investigated, namely helium, hydrogen, nitrogen, and methane. We show that in addition to the direct (gas-kinetic) flux of molecules crossing from the bulk phase on one side of the graphene to the bulk phase on the other side, for gases that adsorb onto the graphene, significant contribution to the flux across the membrane comes from a surface mechanism by which molecules cross after being adsorbed onto the graphene surface. Our results quantify the relative contribution of the bulk and surface mechanisms and show that the direct flux can be described reasonably accurately using kinetic theory, provided the latter is appropriately modified assuming steric molecule-pore interactions, with gas molecules behaving as hard spheres of known kinetic diameters. The surface flux is negligible for gases that do not adsorb onto graphene (e.g., He and H2), while for gases that adsorb (e.g., CH4 and N2) it can be on the order of the direct flux or larger. Our results identify a nanopore geometry that is permeable to hydrogen and helium, is significantly less permeable to nitrogen, and is essentially impermeable to methane, thus validating previous suggestions that nanoporous graphene membranes can be used for gas separation. We also show that molecular permeation is strongly affected by pore functionalization; this observation may be sufficient to explain the large discrepancy between simulated and experimentally measured transport rates through nanoporous graphene membranes.

Implications of Permeation through Intrinsic Defects in Graphene on the Design of Defect-Tolerant Membranes for Gas Separation

Gas transport through intrinsic defects and tears is a critical yet poorly understood phenomenon in graphene membranes for gas separation. We report that independent stacking of graphene layers on a porous support exponentially decreases flow through defects. On the basis of experimental results, we develop a gas transport model that elucidates the separate contributions of tears and intrinsic defects on gas leakage through these membranes. The model shows that the pore size of the porous support and its permeance critically affect the separation behavior, and reveals the parameter space where gas separation can be achieved regardless of the presence of nonselective defects, even for single-layer membranes. The results provide a framework for understanding gas transport in graphene membranes and guide the design of practical, selectively permeable graphene membranes for gas separation.

Fundamental transport mechanisms, fabrication and potential applications of nanoporous atomically thin membranes

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.

Heterogeneous sub-continuum ionic transport in statistically isolated graphene nanopores

Graphene and other two-dimensional materials offer a new class of ultrathin membranes that can have atomically defined nanopores with diameters approaching those of hydrated ions. These nanopores have the smallest possible pore volumes of any ion channel, which, due to ionic dehydration and electrokinetic effects, places them in a novel transport regime and allows membranes to be created that combine selective ionic transport with ultimate permeance and could lead to separations and sensing applications. However, experimental characterization and understanding of sub-continuum ionic transport in nanopores below 2 nm is limited. Here we show that isolated sub-2 nm pores in graphene exhibit, in contrast to larger pores, diverse transport behaviours consistent with ion transport over a free-energy barrier arising from ion dehydration and electrostatic interactions. Current-voltage measurements reveal that the conductance of graphene nanopores spans three orders of magnitude and that they display distinct linear, voltage-activated or rectified current-voltage characteristics and different cation-selectivity profiles. In rare cases, rapid, voltage-dependent stochastic switching is observed, consistent with the presence of a dissociable group in the pore vicinity. A modified Nernst-Planck model incorporating ion hydration and electrostatic effects quantitatively matches the observed behaviours.

Water filtration using plant xylem.

Effective point-of-use devices for providing safe drinking water are urgently needed to reduce the global burden of waterborne disease. Here we show that plant xylem from the sapwood of coniferous trees – a readily available, inexpensive, biodegradable, and disposable material – can remove bacteria from water by simple pressure-driven filtration. Approximately 3 cm3 of sapwood can filter water at the rate of several liters per day, sufficient to meet the clean drinking water needs of one person. The results demonstrate the potential of plant xylem to address the need for pathogen-free drinking water in developing countries and resource-limited settings.

Single-Layer Graphene Membranes Withstand Ultrahigh Applied Pressure

High mechanical strength is essential for pressure-driven membrane separations with nanoporous single-layer graphene, but its ability to withstand high pressures remains to be demonstrated. We monitored failure of centimeter-scale single-layer graphene membranes on porous supports subjected to high pressures. Consistent with theory, the membranes were found to withstand higher pressures when placed on porous supports with smaller pore diameters, but failure occurred over a surprisingly broad range of pressures, attributed to heterogeneous susceptibility to failure at wrinkles, defects, and slack in the suspended graphene. Remarkably, nonwrinkled areas withstood pressure exceeding 100 bar at which many kinds of membrane suffer from compaction. Our study shows that single-layer graphene membranes can sustain ultrahigh pressure especially if the effect of wrinkles is isolated using supports with small pores and suggests the potential for the use of single-layer graphene in high-pressure membrane separations.

Selective Nanoscale Mass Transport across Atomically Thin Single Crystalline Graphene Membranes

Atomically thin single crystals, without grain boundaries and associated defect clusters, represent ideal systems to study and understand intrinsic defects in materials, but probing them collectively over large area remains nontrivial. In this study, the authors probe nanoscale mass transport across large-area (≈0.2 cm2 ) single-crystalline graphene membranes. A novel, polymer-free picture frame assisted technique, coupled with a stress-inducing nickel layer is used to transfer single crystalline graphene grown on silicon carbide substrates to flexible polycarbonate track etched supports with well-defined cylindrical ≈200 nm pores. Diffusion-driven flow shows selective transport of ≈0.66 nm hydrated K+ and Cl- ions over ≈1 nm sized small molecules, indicating the presence of selective sub-nanometer to nanometer sized defects. This work presents a framework to test the barrier properties and intrinsic quality of atomically thin materials at the sub-nanometer to nanometer scale over technologically relevant large areas, and suggests the potential use of intrinsic defects in atomically thin materials for molecular separations or desalting.

Nanoporous Atomically Thin Graphene Membranes for Desalting and Dialysis 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 (cm2 ) 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.