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. Using low-temperature scanning tunneling microscopy on oxidized graphitic lattice, we identify linear chains as bright features that have a threefold symmetry, and which exclusively run along the armchair direction of the lattice confirming the theoretical predictions.

Mechanistic Insights on Functionalization of Graphene with Ozone.

The exposure of graphene to O3 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 O3 strongly physisorbs on graphene with a binding energy of -0.46 eV. It configures in a tilted position with the two terminal O atoms centered above the neighboring graphene honeycombs. A dissociative chemisorption follows by surpassing an energy barrier of 0.75 eV and grafting an epoxy group on graphene reducing the energy of the system by 0.14 eV from the physisorbed state. Subsequent O3 chemisorption is preferred on the same honeycomb, yielding two epoxy groups separated by a single C-C bridge. We show that capturing the onset of spin in oxygen during chemisorption is crucial. We verify this finding with experiments where an exponential increase in the density of epoxy groups as a function of reaction temperature yields an energy barrier of 0.66 eV, in agreement with the DFT prediction. These insights will help efforts to obtain precise patterning of the graphene lattice.

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, Zn2+ and Co2+) 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. However, the state-of-the-art methods yield membranes where ZIF films have thickness exceeding 50 nm. Here we report a crystallization method from ultradilute precursor mixtures, which exploits registry with the underlying crystalline substrate, yielding (within minutes) crystalline ZIF films with thickness down to that of a single structural building unit (2 nm). The film crystallized on graphene has a rigid aperture made of a six-membered zinc imidazolate coordination ring, enabling high-permselective H2 separation performance. The method reported here will probably accelerate the development of two-dimensional metal-organic framework films for efficient membrane separation.

In Situ Nucleation-Decoupled and Site-Specific Incorporation of Å-Scale Pores in Graphene Via Epoxidation.

Generating pores in graphene by decoupled nucleation and expansion is desired to achieve a fine control over the porosity, and is desired to advance several applications. Herein, epoxidation is introduced, which is the formation of nanosized epoxy clusters on the graphitic lattice as nucleation sites without forming pores. In situ gasification of clusters inside a transmission electron microscope shows that pores are generated precisely at the site of the clusters by surpassing an energy barrier of 1.3 eV. Binding energy predictions using ab initio calculations combined with the cluster nucleation theory reveal the structure of the epoxy clusters and indicate that the critical cluster is an epoxy dimer. Finally, it is shown that the cluster gasification can be manipulated to form Å-scale pores which then effectively sieve gas molecules based on their size. This decoupled cluster nucleation and pore formation will likely pave the way for an independent control of pore size and density.

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.g., by transmission electron microscopy. Herein, we utilize a low-temperature scanning tunneling microscope (LT-STM) operating at 4 K to solve the structure of epoxy clusters form upon oxidation. Three distinct nanostructures corresponding to three stages of evolution of vacancy defects are found by quantitatively verifying the experimental data by the van der Waals density functional theory. The smallest cluster is a cyclic epoxy trimer. Their observation validates the theoretical prediction that epoxy trimers minimize the energy in the cyclic structure. The trimers grow into honeycomb superstructures to form larger clusters (1-3 nm). Vacancy defects evolve only in the larger clusters (2-3 nm) in the middle of the cluster, highlighting the role of lattice strain in the generation of vacancies. Semiquinone groups are also present and are assigned at the carbon edge in the vacancy defects. Upon heating to 800 °C, we observe cluster-free vacancy defects resulting from the loss of the entire epoxy population, indicating a reversible functionalization of epoxy groups.

Millisecond lattice gasification for high-density CO2- and O2-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., CO2 from N2 However, rapid etching kinetics needed to achieve the high pore density is challenging to control for such precision. Here, we report a millisecond carbon gasification chemistry incorporating high density (>1012 cm-2) of functional oxygen clusters that then evolve in CO2-sieving vacancy defects under controlled and predictable gasification conditions. A statistical distribution of nanopore lattice isomers is observed, in good agreement with the theoretical solution to the isomer cataloging problem. The gasification technique is scalable, and a centimeter-scale membrane is demonstrated. Last, molecular cutoff could be adjusted by 0.1 Å by in situ expansion of the vacancy defects in an O2 atmosphere. Large CO2 and O2 permeances (>10,000 and 1000 GPU, respectively) are demonstrated accompanying attractive CO2/N2 and O2/N2 selectivities.

Large-scale synthesis of crystalline g-C3N4 nanosheets and high-temperature H2 sieving from assembled films.

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.

Restricting Lattice Flexibility in Polycrystalline Metal-Organic Framework Membranes for Carbon Capture.

Although polycrystalline metal-organic framework (MOF) membranes offer several advantages over other nanoporous membranes, thus far they have not yielded good CO2 separation performance, crucial for energy-efficient carbon capture. ZIF-8, one of the most popular MOFs, has a crystallographically determined pore aperture of 0.34 nm, ideal for CO2 /N2 and CO2 /CH4 separation; however, its flexible lattice restricts the corresponding separation selectivities to below 5. A novel postsynthetic rapid heat treatment (RHT), implemented in a few seconds at 360 °C, which drastically improves the carbon capture performance of the ZIF-8 membranes, is reported. Lattice stiffening is confirmed by the appearance of a temperature-activated transport, attributed to a stronger interaction of gas molecules with the pore aperture, with activation energy increasing with the molecular size (CH4 > CO2 > H2 ). Unprecedented CO2 /CH4 , CO2 /N2 , and H2 /CH4 selectivities exceeding 30, 30, and 175, respectively, and complete blockage of C3 H6 , are achieved. Spectroscopic and X-ray diffraction studies confirm that while the coordination environment and crystallinity are unaffected, lattice distortion and strain are incorporated in the ZIF-8 lattice, increasing the lattice stiffness. Overall, RHT treatment is a facile and versatile technique that can vastly improve the gas-separation performance of the MOF membranes.

Crystallization of gas-selective nanoporous graphene by competitive etching and growth: a modeling study.

A robust synthesis methodology for crystallizing nanoporous single-layer graphene hosting a high density of size-selective nanopores is urgently needed to realize the true potential of two-dimensional membranes for gas separation. Currently, there are no controllable etching techniques for single-layer graphene that are self-limiting, and that can generate size-selective nanopores at a high pore-density. In this work, we simulate a unique chemical vapor deposition based crystallization of graphene on Cu(111), in the presence of an etchant, to generate a high density (>1013 cm-2) of sub-nanometer-sized, elongated nanopores in graphene. An equilibrium between the growth rate and the etching rate is obtained, and beyond a critical time, the total number of the carbon atoms and the edge carbon atoms do not change. Using an optimal first-order etching chemistry, a log-mean pore-size of 5.0 ± 1.7 (number of missing carbon atoms), and a pore-density of 3 × 1013 cm-2 was achieved. A high throughput calculation route for estimating gas selectivity from ensembles of thousands of nanopores was developed. The optimized result yielded H2/CO2, H2/N2 and H2/CH4 selectivities larger than 200, attributing to elongated pores generated by the competitive etching and growth. The approach of competitive etching during the crystal growth is quite generic and can be applied to a number of two-dimensional materials.