Functionalized Graphene Membranes Research Articles

Revealing the role of interlayer spacing in radioactive-ion sieving of functionalized graphene membranes

Functionalization of graphene enables precise control over interlayer spacing during film formation, thereby enhancing the separation efficiency of radioactive ions in graphene membranes. However, the systematic impact of interlayer spacing of graphene membranes on radioactive-ion separation remains unexplored. This study aims to elucidate how interlayer spacing in functionalized graphene membranes affects the separation of radioactive ions. Utilizing polyamidoxime (PAO) to modify graphene oxide, we controlled the interlayer spacing of graphene membranes. Experimental results indicate that tuning interlayer spacing enables control of the permeation flux of radioactive ions (UO22+ 1.01 × 10−5–8.32 × 10−5 mol/m2·h, and K+ remains stable at 3.60 × 10−4 mol/m2·h), and the K+/UO22+ separation factors up to 36.2 at an interlayer spacing of 8.8 Å. Using density functional theory and molecular dynamics simulations, we discovered that the effective separation is mainly determined via interlayer spacing and the quantity of introduced functional groups, explaining the anomalous high permeation flux of target ions at low interlayer spacing (4.3 Å). This study deepens our comprehension of interlayer spacing within nanoconfined spaces for ion separation and recovery via graphene membranes, offering valuable insights for the design and synthesis of high-performance nanomembrane materials.

A theoretical investigation into the effects of functionalized graphene nanosheets on dimethyl sulfoxide separation

The potential of carbon-based nanosheet membranes with functionalized pores is great as water treatment membranes. Using the molecular dynamic simulation technique, the dimethyl sulfoxide (DMSO) separation from the water/DMSO binary solution is investigated, and the functionalized graphene nanosheets are used as a membrane. This membrane was functionalized by –F (fluorine) and –H (hydrogen) functional groups. For the separation of DMSO, external hydrostatic pressures up to 100 MPa were applied to the considered systems. The separation mechanism was based on molecular size. Multiple analyses were done to study the capability of considered membranes for the separation of DMSO molecules from water. The simulation results have indicated that the graphene membrane with various functional groups was impervious to DMSO molecules, and the water molecules were able to permeate across the membrane's pore with high penetrability. In this regard, the water permeability in 100 MPa was obtained at 3915.5 and 3715.3 L m−2. h−1. bar−1 for fluorinated and hydrogenated pore membranes, respectively. These functionalized graphene membranes have high efficiency, and they can be considered effective modules for water/DMSO binary mixture separations.

Coupling solute interactions with functionalized graphene membranes: towards facile membrane-level engineering

Optimizing ion transport through nanoporous graphene membranes with intricate engineering at nanoscale levels finds applications ranging from ion segregation to desalination. Such membrane-level engineering often requires futuristic and state-of-the-art micro- and nanofabrication infrastructure making it less accessible to widespread applications. In this study, the effective membrane pore size is modulated using macroscopic membrane functionalization, which, when combined with the solute concentration, can prove to be facile nanoscale engineering towards achieving selectivity. By performing robust molecular dynamics (MD) simulations of aqueous NaCl solution through a nanoporous graphene membrane, we demonstrate that varying membrane wettability influences the structural organization of ions and water molecules both in the vicinity and inside the nanopore, which is manifested in the form of altered permeation characteristics. Moreover, the disparate solvation characteristics of the ionic species in conjunction with the variable van der Waals interactive forces affect the ion-selective nature (Cl- over Na+) of the membrane. The relative hydrophilization, resulting from the effective functionalization of the nanoporous graphene membrane, not only allows greater control over the permeation characteristics of ions and water molecules mediated by an altered depletion ratio but also gives rise to the ion-selective nature of the membrane, thus providing a sound understanding of the transport properties of ion-water solutions through nanoporous materials.

Enantioseparation processes and mechanisms in functionalized graphene membranes: Facilitated or retarded transport?

Up to date, functionalized graphene-based membranes have exhibited a promising potential in the enantioseparation. However, since precisely controlling the interlayer distance of two-dimensional materials is a great challenge in practical experiments, the transport mechanism of chiral guests in such membranes, together with various critical parameters that play a controlling role in the transport behaviors of the preferentially binding enantiomer in narrow channels, remains to be explored. The molecular dynamics (MD) simulation, especially using the steered MD (SMD) method, might be an alternative way to investigate the enantioseparation processes and mechanisms of layered membranes with different interlayer distances. In this work, D-alanine modified graphene sheets with different interlayer distances were built as membrane models, whereas D- and L-phenylalanine were selected as chiral probes. The effect of the interlayer distance and the applied external force on the enantioseparation performance was examined. Results show that such two parameters exert a significant influence on the enantioseparation performance: (a) Increasing the interlayer distance would result in a conversion from the retarded to the facilitated mechanism at a proper external force (medium); (b) both the large and small driving forces would only lead to the appearance of the retarded transport for the preferential enantiomer, unlike the moderate force; (c) the interaction energy of L-phenylalanine with D-isomer selector decreases with the rising interlayer distances studied in this work, regardless of what the external force is. Our findings can provide guidance on the practical applications in the membrane-based chiral separation.

Bioactive Functionalized Monolayer Graphene for High-Resolution Cryo-Electron Microscopy.

Single-particle cryo-electron microscopy (cryo-EM) has become one of the most essential tools to understand biological mechanisms at molecular level. A major bottleneck in cryo-EM technique is the preparation of good specimens that embed biological macromolecules in a thin layer of vitreous ice. In the canonical cryo-EM specimen preparation method, biological macromolecules tend to be adsorbed to the air-water interface, causing partial denaturation and/or preferential orientations. In this work, we have designed and produced a new type of cryo-EM grids using bioactive-ligand functionalized single-crystalline monolayer graphene membranes as supporting films. The functionalized graphene membrane (FGM) grids exhibit specific binding affinity to histidine (His)-tagged proteins and complexes. In cryo-EM, the FGM grids generate relatively low background for imaging and selectively anchor 20S proteasomes to the supporting film surface, enabling near-atomic-resolution 3D reconstruction of the complex. We envision that the FGM grids could benefit single particle cryo-EM specimen preparation with high reproducibility and robustness, therefore enhancing the efficiency and throughput of high-resolution cryo-EM structural determination.

Ultrafast molecular sieving through functionalized graphene membranes

Graphene shows great promise for advanced filtration membranes with high permeance and enhanced rejection. Here we demonstrate filtration membranes with a nanochannel network for superior separation performance using 100-500 nm-wide graphene nanoplatelets (GnPs) that are efficiently prepared via a green method. The resulting membranes exhibit a well packed layer structure formed by GnPs and are highly stable in water and organic solvents and even in strongly acidic and alkaline media. Moreover, the GnP membranes possess high fluxes and good selectivity in both water and organic solvents based on the small size nanoplatelets and the stable nanochannels between the GnPs. The exfoliated GnPs and the subsequent membranes show great potential for practical applications in water purification and organic solvent filtration.

Fluorine-functionalized nanoporous graphene as an effective membrane for water desalination

Most water in the world is as saline water in seas and oceans. Desalination technology is a promising method to solve the global water crisis. Recently, many attentions have been paid to the graphene-based membranes in water desalination due to their low production cost and high efficiency. In this paper, molecular dynamics simulations are employed to investigate the effect of functionalized graphene nanosheet (GNS) membranes on the performance of salt separation from seawater in terms of water permeability and salt rejection. For this purpose, the hydrogenated (–H) and fluorinated (–F) pores were created on the GNS membrane. Then, the functionalized graphene membrane was placed in the middle of the simulation box in an aqueous ionic solution containing Na+ and Cl− ions. The applied pressure (in the range of 10–100 MPa) was used as the driving force for transport of water molecules across the reverse osmosis (RO) graphene-based membrane in order to obtain the water permeability and salt rejection. Also, radial distribution functions (RDFs) of ion–water and water–water as well as the water density map around the membrane were obtained. The results indicated that the hydrophilic chemical functions such as fluorine (–F) can improve the water permeability at low pressures.

Computational study on the ability of functionalized graphene nanosheet for nitrate removal from water

Graphene sheets as nanostructured membranes with various functional groups (fluorine or hydrogen atoms) and different pore sizes were studied to separate nitrate anions from water molecules using molecular dynamics simulation method. Three systems with different functionalized graphene membranes were simulated to purified water from contamination. These three functionalized graphenes which two of them had fluorinated graphene pores with various diameters and one of them had hydrogenated graphene pore that its pore size was smaller than one of the fluorinated graphene pores, were located at the middle of the simulation boxes which contained sodium nitrate aqueous solution. Water molecules crossed from all functionalized graphenes but nitrate ions only passed across the fluorinated graphene with large size pore. In addition to the exerted pressures and the sizes of the graphene pores, the type of the functional groups based on their chemical nature had influence on water permeation and ion rejection.

A Continuum Damage Model for Functionalized Graphene Membranes Based on Atomistic Simulations

A continuum model for GO membranes is developed in this study. The model is built representing the membrane as a two-dimensional, heterogeneous, two-phase continuum and the constitutive behavior of each phase (graphitic or oxidized) is built based on DFTB simulations of representative patches. A hyper-elastic continuum model is employed for the graphene areas, while a continuum damage model is more adequate for representing the behavior of oxidized regions. A finite element implementation for GO membranes subjected to degradation and failure is then implemented and, to avoid localization instabilities and spurious mesh sensitivity, a simple crack band model is adopted. The developed implementation is then used to investigate the existence of GO nano-representative volume elements.

Theoretical investigation of gas separation in functionalized nanoporous graphene membranes

Graphene has enormous potential as a membrane-separation material with ultrahigh permeability and selectivity. The understanding of mass-transport mechanism in graphene membranes is crucial for applications in gas separation field. We computationally investigated the capability and mechanisms of functionalized nanoporous graphene membranes for gas separation. The functionalized graphene membranes with appropriate pore size and geometry possess excellent high selectivity for separating CO2/N2, CO2/CH4 and N2/CH4 gas mixtures with a gas permeance of ∼103–105 GPU, compared with ∼100 GPU for typical polymeric membranes. More important, we found that, for ultrathin graphene membranes, the gas separation performance has a great dependence not only with the energy barrier for gas getting into the pore of the graphene membranes, but also with the energy barrier for gas escaping from the pore to the other side of the membranes. The gas separation performance can be tuned by changing the two energy barriers, which can be realized by varying the chemical functional groups on the pore rim of the graphene. The novel mass-transport mechanism obtained in current study may provide a theoretical foundation for guiding the future design of graphene membranes with outstanding separation performance.

Molecular dynamics study on water desalination through functionalized nanoporous graphene

Molecular dynamics simulations were employed to investigate water desalination through functionalized nanoporous graphene membranes. Six graphene membranes were considered in which the carbon atoms of the pores were terminated by hydrogen or hydroxyl functional groups. The results demonstrate that water desalination occurs under external pressure and water flux permeating the membranes scales linearly with external pressure and pore diameter. The hierarchy of water flux through the functionalized graphene membranes was explained by potential of mean force. The salt rejection from smallest pore was 100% and decreases as pore diameter increases. Both Na+ and Cl− ions permeate through membrane with the largest pore, and the selectivity of the ions permeating exhibits a significant correlation with functional group. The designed graphene membrane shows excellent performance in terms of both salt rejection and water transport. Ultrahigh water permeance of 785.6 L per m2·h·bar obtained is two or three orders of magnitude higher than current commercially available reverse osmosis (RO) and nanofiltration membranes. This simulation study provides a microscopic insight into water desalination in various functionalized graphene membranes and reveals governing factor for water flux and also suggests a potential candidate as a RO membrane.

Pyridinic nitrogen doped nanoporous graphene as desalination membrane: Molecular simulation study

Functionalized nanoporous graphene has shown great promise as emerging membrane. Herein, we computationally demonstrate the separation performance using pyridinic-like nitrogen doped nanoporous graphene as reverse osmosis desalination membrane. The water permeation and salt rejection of the functionalized graphene membranes with various nitrogen-doping levels were simulated and characterized. We show that all functionalized graphenes investigated in this work exhibit higher water flux and acceptable salt rejection. In particular, the NOH graphene membrane with partial hydroxyl group inclusion shows excellent desalination efficiency. The interfacial properties of water and ions, as well as their free energy landscapes in passing through the graphene nanopores have been simulated in order to explore the desalination mechanism. The moderate free energy barriers for water passages confirm larger water fluxes in the functionalized graphene membranes. It was revealed that the salt rejection for the functionalized graphenes is the pore size exclusion of hydrated ions and the charged repulsion from pore surfaces is not the main factor. Overall, our results indicate that pyridinic-like nitrogen doped graphenes have a significant potential as nanostructured desalination membranes.

Selective Ion Transport through Functionalized Graphene Membranes Based on Delicate Ion–Graphene Interactions

Recently, graphene oxide (GO) membranes have been reported with the ability to separate different solutes in aqueous suspensions by a molecular sieving effect. On the other hand, we propose that the chemical interactions between ions and GO membranes might also take effect in selective ion transmembrane transportation. In this paper, on the basis of the permeation of Cu2+ and Mg2+ sources through hydroxyl-, carboxyl-, and amino-functionalized graphene membranes, the delicate ion–graphene interactions which might be responsible for the selective ion permeation are investigated. We demonstrate experimentally that the coordination between transition-metal cations and carboxyl functionalities and the cation−π interactions between main-group cations and sp2 regions are responsible for the selective transport of small ions through graphene-based membranes, which is beyond the scope of molecular sieving effect proposed previously. Notably, by grafting amino groups onto the graphene basal planes, the permeations ...

Functionalized graphene as a nanostructured membrane for removal of copper and mercury from aqueous solution: A molecular dynamics simulation study

The purpose of the present study was to investigate the removal of copper and mercury using functionalized graphene as a nanostructured membrane. The molecular dynamics simulation method was used to investigate the removal ability of these ions from aqueous solution using functionalized graphene membrane. The studied systems included a functionalized graphene membrane which was placed in the aqueous ionic solution of CuCl2 and HgCl2. An external electrical field was applied along the z axis of the system. The results indicated that the application of electrical field on the system caused the desired ions to pass through the functionalized graphene membrane. The Fluorinated pore (F-pore) terminated graphene selectively conducted Cu2+ and Hg2+ ions. The calculation of the potential of mean force of ions revealed that Cu2+ and Hg2+ ions face a relatively small energy barrier and could not pass through the F-pore graphene unless an external electrical field was applied upon them. In contrast, the energy barrier for the Cl− ion was large and it could not pass through the F-pore graphene. The findings of the study indicate that the permeation of ions across the graphene was a function of applied electrical fields. The findings of the present study are based on the detailed analysis and consideration of potential of mean force and radial distribution function curves.

Nanoporous Graphene Membranes for Efficient3He/4He Separation

Nanoporous functionalized graphene membranes containing nitrogen atoms in a nanosized ring pore have the capability to separate 3He from 4He efficiently by quantum tunneling through the pore. Calculations on size-reduced model systems of single-graphene pores reveal that a balanced choice of tunneling barrier height and low gas temperature boosts the selectivity and keeps the helium gas flux at an industrially exploitable level.