Angstrom-Scale Triangular Pore in Single-Layer Hexagonal Boron Nitride Membrane for Molecular Sieving.

Single-layer crystalline films are ideal separation membrane materials because their atomic thickness could yield the highest possible molecular flux once nanopores are generated. However, the development of single-layer membranes with well-defined pore structures remains elusive, which makes the realization of efficient molecular sieving and interpretation of molecular transport a difficult task. Herein, we report the fabrication of single-layer nanoporous hexagonal boron nitride (hBN) membranes that uniquely contain triangular nanopores with a high density (around 10 pores per cm).

Gated CO permeation across dynamic graphene pores.

Oxidation of graphene has been successfully used to incorporate semiquinone (C = O)-functionalized Å-scale pores, yielding attractive carbon capture performance. However, the true potential of such pores has remained unclear due to a lack of dedicated mechanistic studies. Herein, using molecular dynamics (MD) simulations, we show that C = O displays a strong molecular-interaction-dependent dynamic motion, leading to a distribution in the pore limiting diameter (PLD), comparable to the size differences between CO, O, and N.

A molecularly engineered large-area nanoporous atomically thin graphene membrane for ion separation.

Atomically thin graphene membranes with sub-1-nm pores show promise for ion/molecular separation, osmotic energy generation, and energy storage. Narrowing the pore size distribution and controlling the surface charge are essential to achieve these applications. However, nanoporous graphene membranes fabricated via conventional methods possess a broad pore size distribution and inadequately regulated surface charge, limiting their applications.

Non-van-der-Waals Oriented Two-Dimensional UiO-66 Films by Rapid Aqueous Synthesis at Room Temperature.

The synthesis of MOFs in a two-dimensional (2D) film morphology is attractive for several applications including molecular and ionic separation. However, 2D MOFs have only been reported from structures that crystallize in lamellar morphology, where layers are held together by van der Waals (vdW) interaction. By comparison, UiO-66, one of the most studied MOFs because of its exceptional chemical stability, has only been reported in three-dimensional (3D) morphology.

High-performance H/CO separation from 4-nm-thick oriented Zn(benzimidazole) films.

High-performance membrane-based H/CO separation offers a promising way to reduce the energy costs of precombustion capture. Current membranes, often made from two-dimensional laminates like metal-organic frameworks, have limitations due to complex fabrication methods requiring high temperatures, organic solvents, and long synthesis time. These processes often result in poor H/CO selectivity under pressurized conditions due to defective transport pathways.

Electrochemical-repaired porous graphene membranes for precise ion-ion separation.

The preparation of atom-thick porous lattice hosting Å-scale pores is attractive to achieve a large ion-ion selectivity in combination with a large ion flux. Graphene film is an ideal selective layer for this if high-precision pores can be incorporated, however, it is challenging to avoid larger non-selective pores at the tail-end of the pore size distribution which reduces ion-ion selectivity. Herein, we develop a strategy to overcome this challenge using an electrochemical repair strategy that successfully masks larger pores in large-area graphene.

Advancing Molecular Sieving via Å-Scale Pore Tuning in Bottom-Up Graphene Synthesis.

Porous graphene films are attractive as a gas separation membrane given that the selective layer can be just one atom thick, allowing high-flux separation. A favorable aspect of porous graphene is that the pore size, essentially gaps created by lattice defects, can be tuned. While this has been demonstrated for postsynthetic, top-down pore etching in graphene, it does not exist in the more scalable, bottom-up synthesis of porous graphene.

Tuning Pore Size in Graphene in the Angstrom Regime for Highly Selective Ion-Ion Separation.

Zero-dimensional pores spanning only a few angstroms in size in two-dimensional materials such as graphene are some of the most promising systems for designing ion-ion selective membranes. However, the key challenge in the field is that so far a crack-free macroscopic graphene membrane for ion-ion separation has not been realized. Further, methods to tune the pores in the Å-regime to achieve a large ion-ion selectivity from the graphene pore have not been realized.

Dynamic Behavior of Spatially Confined Sn Clusters and Its Application in Highly Efficient Sodium Storage with High Initial Coulombic Efficiency.

Advanced battery electrodes require a cautious design of microscale particles with built-in nanoscale features to exploit the advantages of both micro- and nano-particles relative to their performance attributes. Herein, the dynamic behavior of nanosized Sn clusters and their host pores in carbon nanofiber) during sodiation and desodiation is revealed using a state-of-the-art 3D electron microscopic reconstruction technique. For the first time, the anomalous expansion of Sn clusters after desodiation is observed owing to the aggregation of clusters/single atoms.

Mechanistic Insights on Functionalization of Graphene with Ozone.

The exposure of graphene to O results in functionalization of its lattice with epoxy, even at room temperature. This reaction is of fundamental interest for precise lattice patterning, however, is not well understood. Herein, using van der Waals density functional theory (vdW-DFT) incorporating spin-polarized calculations, we find that O strongly physisorbs on graphene with a binding energy of -0.

Unraveling the Oxidation of a Graphitic Lattice: Structure Determination of Oxygen Clusters.

Unraveling the oxidation of graphitic lattice is of great interest for atomic-scale lattice manipulation. Herein, we build epoxy cluster, atom by atom, using Van der Waals' density-functional theory aided by Clar's aromatic π-sextet rule. We predict the formation of cyclic epoxy trimers and its linear chains propagating along the armchair direction of the lattice to minimize the system's energy.

Selective Photonic Gasification of Strained Oxygen Clusters on Graphene for Tuning Pore Size in the Å Regime.

Controlling the size of single-digit pores, such as those in graphene, with an Å resolution has been challenging due to the limited understanding of pore evolution at the atomic scale. The controlled oxidation of graphene has led to Å-scale pores; however, obtaining a fine control over pore evolution from the pore precursor (i.e.

Unit-cell-thick zeolitic imidazolate framework films for membrane application.

Zeolitic imidazolate frameworks (ZIFs) are a subset of metal-organic frameworks with more than 200 characterized crystalline and amorphous networks made of divalent transition metal centres (for example, Zn and Co) linked by imidazolate linkers. ZIF thin films have been intensively pursued, motivated by the desire to prepare membranes for selective gas and liquid separations. To achieve membranes with high throughput, as in ångström-scale biological channels with nanometre-scale path lengths, ZIF films with the minimum possible thickness-down to just one unit cell-are highly desired.

Gas Separation Membranes with Atom-Thick Nanopores: The Potential of Nanoporous Single-Layer Graphene.

Gas separation is one of the most important industrial processes and is poised to take a larger role in the transition to renewable energy, e.g., carbon capture and hydrogen purification.

Enhanced Water Evaporation from Å-Scale Graphene Nanopores.

Enhancing the kinetics of liquid-vapor transition from nanoscale confinements is an attractive strategy for developing evaporation and separation applications. The ultimate limit of confinement for evaporation is an atom thick interface hosting angstrom-scale nanopores. Herein, using a combined experimental/computational approach, we report highly enhanced water evaporation rates when angstrom sized oxygen-functionalized graphene nanopores are placed at the liquid-vapor interface.

Unblocking Ion-occluded Pore Channels in Poly(triazine imide) Framework for Proton Conduction.

Poly(triazine imide) or PTI is an ordered graphitic carbon nitride hosting Å-scale pores attractive for selective molecular transport. AA'-stacked PTI layers are synthesized by ionothermal route during which ions occupy the framework and occlude the pores. Synthesis of ion-free PTI hosting AB-stacked layers has been reported, however, pores in this configuration are blocked by the neighboring layer.

Structure Evolution of Graphitic Surface upon Oxidation: Insights by Scanning Tunneling Microscopy.

Oxidation of graphitic materials has been studied for more than a century to synthesize materials such as graphene oxide, nanoporous graphene, and to cut or unzip carbon nanotubes. However, the understanding of the early stages of oxidation is limited to theoretical studies, and experimental validation has been elusive. This is due to (i) challenging sample preparation for characterization because of the presence of highly mobile and reactive epoxy groups formed during oxidation, and (ii) gasification of the functional groups during imaging with atomic resolution, e.

Demonstrating and Unraveling a Controlled Nanometer-Scale Expansion of the Vacancy Defects in Graphene by CO.

A controlled manipulation of graphene edges and vacancies is desired for molecular separation, sensing and electronics applications. Unfortunately, available etching methods always lead to vacancy nucleation making it challenging to control etching. Herein, we report CO -led controlled etching down to 2-3 Å per minute while completely avoiding vacancy nucleation.

Bottom-up synthesis of graphene films hosting atom-thick molecular-sieving apertures.

Incorporation of a high density of molecular-sieving nanopores in the graphene lattice by the bottom-up synthesis is highly attractive for high-performance membranes. Herein, we achieve this by a controlled synthesis of nanocrystalline graphene where incomplete growth of a few nanometer-sized, misoriented grains generates molecular-sized pores in the lattice. The density of pores is comparable to that obtained by the state-of-the-art postsynthetic etching (10 cm) and is up to two orders of magnitude higher than that of molecular-sieving intrinsic vacancy defects in single-layer graphene (SLG) prepared by chemical vapor deposition.

Multipulsed Millisecond Ozone Gasification for Predictable Tuning of Nucleation and Nucleation-Decoupled Nanopore Expansion in Graphene for Carbon Capture.

Predictable and tunable etching of angstrom-scale nanopores in single-layer graphene (SLG) can allow one to realize high-performance gas separation even from similar-sized molecules. We advance toward this goal by developing two etching regimes for SLG where the incorporation of angstrom-scale vacancy defects can be controlled. We screen several exposure profiles for the etchant, controlled by a multipulse millisecond treatment, using a mathematical model predicting the nucleation and pore expansion rates.

Mechanistic Study on Thermally Induced Lattice Stiffening of ZIF-8.

The flexibility of the ZIF-8 aperture, which inhibits a molecular cutoff of 3.4 Å, can be reduced by rapid heat treatment to obtain CO-selective membranes. However, the early stages of the structural, morphological, and chemical changes responsible for the lattice rigidification remain elusive.

Millisecond lattice gasification for high-density CO- and O-sieving nanopores in single-layer graphene.

Etching single-layer graphene to incorporate a high pore density with sub-angstrom precision in molecular differentiation is critical to realize the promising high-flux separation of similar-sized gas molecules, e.g., CO from N However, rapid etching kinetics needed to achieve the high pore density is challenging to control for such precision.

Gas-sieving zeolitic membranes fabricated by condensation of precursor nanosheets.

The synthesis of molecular-sieving zeolitic membranes by the assembly of building blocks, avoiding the hydrothermal treatment, is highly desired to improve reproducibility and scalability. Here we report exfoliation of the sodalite precursor RUB-15 into crystalline 0.8-nm-thick nanosheets, that host hydrogen-sieving six-membered rings (6-MRs) of SiO tetrahedra.

Ultrathin permselective membranes: the latent way for efficient gas separation.

Membrane gas separation has attracted the attention of chemical engineers for the selective separation of gases. Among the different types of membranes used, ultrathin membranes are recognized to break the trade-off between selectivity and permeance to provide ultimate separation. Such success has been associated with the ultrathin nature of the selective layer as well as their defect-free structure.