Nanoporous Graphene Research Articles

Undifferentiated Permeation of Long-Chain Hydrocarbon Molecules through Graphene Nanopores and Its Implications for Alkane Separations

Undifferentiated Permeation of Long-Chain Hydrocarbon Molecules through Graphene Nanopores and Its Implications for Alkane Separations

Molecular simulation of confined ethaline‐based deep eutectic solvents for separations of carbon dioxide from methane

AbstractClassical molecular dynamics (MD) simulations were used to study the separation of carbon dioxide from methane by three formulations of the deep eutectic solvent (DES) ethaline (choline chloride: ethylene glycol at 1:2, 1:4, and 1:8 molar ratios), confined inside graphite and titania (rutile) slit pores of two different pore widths, 2 and 5 nm. In addition, equivalent DES systems in the bulk were studied, which can also be viewed as a model supported DES membrane with μm‐sized pores. Our results indicate that variations in the ratio of ethylene glycol, which in turn affect the interactions of all DES species with the gas molecules and the different pore walls, plus confinement effects resulting from varying the pore sizes, can affect the gas separation performance of these systems in complex ways. The highest permselectivities (~20), computed as the product of the diffusivity and solubility selectivities, are observed for 1:2 ethaline in a 5 nm graphite pore, followed by the 1:4 DES in a 5 nm graphite pore, 1:2 ethaline in a 2 nm graphite pore, and the 1:8 bulk DES. In bulk systems, all three selectivities reach their highest values for 1:8 ethaline. When the DESs are confined in the nanopores, the solubility selectivity for most systems improves compared to the equivalent bulk systems, with the graphite pores having the largest solubility selectivities for any given ethylene glycol ratio. In contrast, the diffusivity selectivities in confined systems tend to be similar to the values observed in the bulk DESs. Interaction energies and local density profiles were used to rationalize absorption and diffusivity of gases in our systems. Confining ethaline in graphite and rutile nanopores tends to weaken the CO2‐ethylene glycol and CO2‐cation interactions compared to the values observed in equivalent bulk ethaline systems, which also affect the local density profiles. Our results confirm that variations in ethylene glycol ratio, pore size, and pore wall material can lead to significant changes in gas separation performance. Other porous matrices, for example, nanoporous polymer formulations and graphene oxides, should be considered in follow‐up studies as they may lead to significant improvements in gas separation performance as compared to the bulk DES.

Molecular Bridge Engineering for Tuning Quantum Electronic Transport and Anisotropy in Nanoporous Graphene

Recent advances on surface-assisted synthesis have demonstrated that arrays of nanometer wide graphene nanoribbons can be laterally coupled with atomic precision to give rise to a highly anisotropic nanoporous graphene structure. Electronically, this graphene nanoarchitecture can be conceived as a set of weakly coupled semiconducting 1D nanochannels with electron propagation characterized by substantial interchannel quantum interferences. Here, we report the synthesis of a new nanoporous graphene structure where the interribbon electronic coupling can be controlled by the different degrees of freedom provided by phenylene bridges that couple the conducting channels. This versatility arises from the multiplicity of phenylene cross-coupling configurations, which provides a robust chemical knob, and from the interphenyl twist angle that acts as a fine-tunable knob. The twist angle is significantly altered by the interaction with the substrate, as confirmed by a combined bond-resolved scanning tunneling microscopy (STM) and ab initio analysis, and should accordingly be addressable by other external stimuli. Electron propagation simulations demonstrate the capability of either switching on/off or modulating the interribbon coupling by the corresponding use of the chemical or the conformational knob. Molecular bridges therefore emerge as efficient tools to engineer quantum transport and anisotropy in carbon-based 2D nanoarchitectures.

Pump-Probe X-ray Photoemission Spectroscopy of Free-Standing Graphane

Free-standing nanoporous graphene was hydrogenated at about 60 at.% H uptake, as determined by the emerging of the sp3 bonding component in the C 1s core level investigated by high-resolution X-ray photoelectron spectroscopy (XPS). Fully unsupported graphane was investigated by XPS under optical excitation at 2.4 eV. At a laser fluence of 1.6 mJ/cm2, a partial irreversible dehydrogenation of the graphane was observed, which could be attributed either to the local temperature increase or to a photo-induced softening of the H-to-C stretching mode. The sub-ns dynamics of the energy shift and peak broadening of the C 1s core level revealed two different decay constants: 210 ps and 130 ps, respectively, the former associated with photovoltage dynamics and the latter with thermal heating on a time scale comparable with the synchrotron temporal resolution.

Nanoporous multilayer graphene oxide membrane for forward osmosis metal ion recovery from spent Li-ion batteries

The recovery of Li and rare metals from the spent electrodes of Li-ion batteries (LIBs) is becoming increasingly important. Herein, nanoporous multilayer graphene oxide (NMG) membranes were fabricated via the confined thermal annealing method to achieve Li-ion selectivity. A graphene oxide (GO) membrane was prepared by coating the membrane with an aqueous layer of GO liquid crystal via the scalable bar coating method, followed by hot-pressing. The influence of the GO interlayer spacing and nanopore presence on the ion separation performance was investigated. The NMG membrane shows different ion permeance phenomena depending on ion concentration. The permeation rate of divalent ions (Co, Ni, Mn) through the NMG membrane was faster than that of Li ions in solution with low ionic strength, whereas the membrane was Li-ion selective in mixed ionic solutions or at high ionic strength. This result indicates that electrostatic interaction by oxygen groups is important at low ionic strength, but size exclusion by interlayer spacing and adsorption by nanopore is critical at high ionic strength. The ion permeation mechanisms were further examined based on molecular calculations, which revealed that the binding energies between the divalent ions and nanopores or basal plane of graphene were high, resulting in slow ion permeation. When the NMG membrane was combined in a forward osmosis system, Li-ion can be separated continuously from the mixture solution simulated from the spent Li-battery electrode. This approach shows the high potential of nanoporous multilayer graphene membrane for Li extraction in particular with dense pore structure and around 7 Å of d-spacing.

Scalable fabrication of nanoporous multilayer graphene oxide membrane for organic solvent nanofiltration

Nanoporous graphene is promising for the fabrication of high-performance organic solvent nanofiltration (OSN) membranes owing to the excellent chemical resistance of graphene in organic solvents. Moreover, the nanopores increase solvent permeance by providing diffusion channels. However, conventional chemical and physical etching methods are generally applicable on a laboratory-scale, and the large-scale fabrication of these structures is challenging. Herein, a large-area nanoporous multilayer graphene oxide (NMG) membrane was prepared using a combination of slot-die coating and confined thermal treatment. Graphene oxide (GO) was coated on polymeric supports using a slot-die coater, which is generally used for continuous coating in industry. Afterward, the GO membrane was treated using a hot-pressing method to activate the nanopores on the graphene surface and weld the polymeric support with the graphene layer. The interlayer and pore structure of GO were tuned by modulating the hot-pressing time, and its influence on OSN performance was systemically investigated. The optimized NMG membrane exhibited a high ethanol permeance of 300 Lm−2h−1bar−1 and a sharp molecular weight cut-off of 500 g/mol. Furthermore, the enhanced adhesion between graphene and the polymeric support enables mechanically stable membrane operation under cross-flow conditions for 30 days, which is the longest test time reported for two-dimensional material-based OSN membranes thus far.

Generating nano-incised graphene kirigami membrane via selective tearing

By virtue of its single-layer thickness, nanoscale incisions and flexible structure, graphene kirigami (GK) owns a great prospect to be an ultra-permeable membrane for separation engineering. However, the difficulty in creating nanoscale incisions has prevented GK from being considered as a membrane candidate in the past. This situation has been improved recently by some emerging kirigami-inspired synthetic strategies and techniques for constructing complex three-dimensional nanostructures. Here, we reveal the potential fabrication of nano-incised GK membranes via an innovative selective tearing method using molecular dynamics simulation. The results exhibit that through the selective tearing method, the periodic wrinkles could be generated on the defective graphene, contributing to the stress concentration around the defects and causing the CC bonds to break, finally forming nano-incisions. The initial defective graphene, including its size, defects density, parallelogram angle and aspect ratio, as well as the shear angle, are crucial to the incision distribution on the formed GK-like membrane after selecting tearing treatment. The desalination simulation demonstrates that the selective tearing formed graphene kirigami (STGK) membrane has ultra-high water permeability, achieving 1197 L/m2/h/bar with 100 % salt rejection, 5.2–6.3 times higher than the previously reported nanoporous graphene and more than two orders of magnitude higher than current reverse osmosis membranes. We expect this work will inspire the next-generation membranes for separation and purification technology.

Microwave-assisted design of nanoporous graphene membrane for ultrafast and switchable organic solvent nanofiltration

Layered two-dimensional materials can potentially be utilized for organic solvent nanofiltration (OSN) membrane fabrication owing to their precise molecular sieving by the interlayer structure and excellent stability in harsh conditions. Nevertheless, the extensive tortuosity of nanochannels and bulky solvent molecules impede rapid permeability. Herein, nanoporous graphene (NG) with a high density of sp2 carbon domain was synthesized via sequential thermal pore activation of graphene oxide (GO) and microwave-assisted reduction. Due to the smooth sp2 carbon domain surfaces and dense nanopores, the microwave-treated nanoporous graphene membrane exhibited ultrafast organic solvent permeance (e.g., IPA: 2278 LMH/bar) with excellent stability under practical cross-flow conditions. Furthermore, the membrane molecular weight cut-off (MWCO) is switchable from 500 Da size of molecule to sub-nanometer-size molecules depending on the solvent type, and this switching occurs spontaneously with solvent change. These properties indicate feasibility of multiple (both binary and ternary) organic mixture separation using a single membrane. The nanochannel structure effect on solvent transport is also investigated using computation calculations.

Development of an Artificially Intelligent Nanopore for High-Throughput DNA Sequencing with a Machine-Learning-Aided Quantum-Tunneling Approach.

Solid-state nanopore-based single-molecule DNA sequencing with quantum tunneling technology poses formidable challenges to achieve long-read sequencing and high-throughput analysis. Here, we propose a method for developing an artificially intelligent (AI) nanopore that does not require extraction of the signature transmission function for each nucleotide of the whole DNA strand by integrating supervised machine learning (ML) and transverse quantum transport technology with a graphene nanopore. The optimized ML model can predict the transmission function of all other nucleotides after training with data sets of all the orientations of any nucleotide inside the nanopore with a root-mean-square error (RMSE) of as low as 0.062. Further, up to 96.01% accuracy is achieved in classifying the unlabeled nucleotides with their transmission readouts. We envision that an AI nanopore can alleviate the experimental challenges of the quantum-tunneling method and pave the way for rapid and high-precision DNA sequencing by predicting their signature transmission functions.

Mechanisms of lithium selection from mixed LiCl-NaCl solution by nanopores: The synergistic effects of nanoconfinement and electric fields

In this work, molecular dynamics simulations were performed to investigate the separation mechanism of Na+/Li+ by graphene nanopores under different electric fields and concentrations. The results showed that the Li+ selectivity of nanopores can mainly be attributed to the association-dissociation mechanism near nanopores and not the dehydration of Na+/Li+. Ions will pass through three typical regions near nanopores: the low ion association region, high ion association region, and high water density region. Abnormal enhancement of ion association occurs on cation side near nanopores, which can be attributed to the difference of ion transports under confinement. The association-dissociation dynamics of Na+/Li+ and Cl− near nanopores can be significantly affected by adjusting the electric field intensity and pore size. In contrast, the effect of ion concentration on ion selectivity is less obvious. Due to the confinement of nanopores, the association of cations and anions near nanopores will be enhanced. Meanwhile, ions need to dissociate from ion-associated species before being transported through nanopores. Thus, ion permeation will be affected by the ion association degree as well as the stability of ion-associated species.

Theoretical investigation of graphene kirigami membrane for natural gas processing

Membrane separation technology plays a vital role in natural gas processing due to its cost-effectiveness, excellent efficiency and low energy consumption. In this study, we demonstrate the superior permeability and selection capability of the graphene kirigami (GK) membrane for natural gas purification via molecular dynamics insights. The results indicate that the separation rate of the GK membrane can reach up to 4.1 × 106 GPU (gas permeance unit) with nearly 100% selectivity of the permeating gases mixture (H2S, CO2 and N2) over the non-permeating gas (CH4). Furthermore, the Monte Carlo simulation reveals that the unique geometry of the GK structure introduces a funnel-shaped adsorption channel to guide specific molecules’ separation and enhance the efficiency of the membrane. Compared with the nano-porous graphene (NPG) membrane, the gas separation rate of the GK membrane can be increased by more than four times. Moreover, the GK membrane does not require the modification of functional groups in natural gas purification, which provides great convenience for future applications in practical projects. The considerable potential of the GK membrane underpinned by the findings of this study will attract broad interest in the field of separation and purification.

Atomic boundary position and steric effects on ion transport and separation through nanoporous graphene membrane

Atomic boundary position and steric effects on ion transport and separation through nanoporous graphene membrane

Enumerating Stable Nanopores in Graphene and Their Geometrical Properties Using the Combinatorics of Hexagonal Lattices

Nanopores in two-dimensional (2D) materials, including graphene, can be used for a variety of applications, such as gas separations, water desalination, and DNA sequencing. So far, however, all plausible isomeric shapes of graphene nanopores have not been enumerated. Instead, a probabilistic approach has been followed to predict nanopore shapes in 2D materials, due to the exponential increase in the number of nanopores as the size of the vacancy increases. For example, there are 12 possible isomers when N = 6 atoms are removed, a number that theoretically increases to 11.7 million when N = 20 atoms are removed from the graphene lattice. In this regard, the development of a smaller, exhaustive data set of stable nanopore shapes can help future experimental and theoretical studies focused on using nanoporous 2D materials in various applications. In this work, we use the theory of 2D triangular "lattice animals" to create a library of all stable graphene nanopore shapes based on a modification of a well-known algorithm in the mathematical combinatorics of polyforms known as Redelmeier's algorithm. We show that there exists a correspondence between graphene nanopores and triangular polyforms (called polyiamonds) as well as hexagonal polyforms (called polyhexes). We develop the concept of a polyiamond ID to identify unique nanopore isomers. We also use concepts from polyiamond and polyhex geometries to eliminate unstable nanopores containing dangling atoms, bonds, and moieties. We verify using density functional theory calculations that such pores are indeed unstable. The exclusion of these unstable nanopores leads to a remarkable reduction in the possible nanopores from 11.7 million for N = 20 to only 0.184 million nanopores, thereby indicating that the number of stable nanopores is almost 2 orders of magnitude lower and is much more tractable. Not only that, by extracting the polyhex outline, our algorithm allows searching for nanopores with dimensions and shape factors in a specified range, thus aiding the design of the geometrical properties of nanopores for specific applications. We also provide the coordinate files of the stable nanopores as a library to facilitate future theoretical studies of these nanopores.

Design of Porous Graphene Materials from Organic Precursors

AbstractThe preparation of the porous graphene materials with controllable porosity basically depends on the design of porous architectures. The development of three‐dimensional (3D) graphene materials from two‐dimensional (2D) graphene sheets can harness the unique physical and electrical properties of graphene, but the challenges lie on the design and synthesis of nanoporous graphene with controlled engineering. In this work, two organic aromatic molecules viz., 2‐amino‐3‐hydroxypyridine and phloroglucinol were targeted for the development of porous graphene nanostructures. The synthesis process was designed in such a way that both the molecules having ─OH and ─NH2 groups at ortho position and 3 ─OH groups at 1, 3, 5 positions, respectively, can generate pores along with the development of graphenic lattice during heat treatment. The optimization of reaction conditions viz., time and temperature was done and the chemistry of formation of porous natured graphenic lattice was discussed. Interestingly, the results indicate that both the organic molecules have the potential to develop porous graphenic structures within their lattice at relatively low temperatures without using any additional reagents and reaction conditions. It is suggested that the structure of organic precursor is a critical factor which needs to be optimized to produce porous graphenes.

Surface defect healing in annealing from nanoporous carbons to nanoporous graphenes.

Nanoporous graphene (NPG) materials have the pronounced electrochemical stability of the seamless graphene structures developed over the 3D space. We revisited the Raman spectra of nanoporous carbons (NPCs) synthesized using θ-/γ-Al2O3 templates and NPGs converted from NPCs by annealing at 1800 °C to identify the type and density of defects. We found that both the NPCs and NPGs mostly consist of single-layered graphene with a few single vacancies and Stone-Wales defects. The density of vacancy defect per hexagon in the graphene sheet is estimated to be 10-2 for NPCs, while the annealing reduced the value to 10-3-10-4 for NPGs. This supports the outstanding chemical and electrochemical stability of the novel porous carbon materials.

A study of the permeation barrier of nanoporous Graphene

Nanoporous Graphene, due to its single atom thickness and good mechanical strength is an emerging candidate for efficient and reliable gas separation applications. The permeation of the gas molecules through the pores can be seen as an activated process, whereby the gas molecules have to overcome a threshold barrier before it can pass through the pore. Here, we study and compare the Single Point Energy of the CO2 molecule as it approaches a nanoporous Graphene sheet comprising of 6 Carbon atoms removed contiguously to create what is known as the Type A nanopore. The distance of the single molecule from the pore is varied continuously for 2 configurations of the gas molecule, one parallel and other perpendicular to the nanopore, positioned vertically above the centre of the 6-pore, by means of ab-initio simulations based on Density Functional Theory. The permeation barrier of the CO2 molecule is estimated. It is found that orientation of incident molecule along with the pore geometry, plays an important role in gas permeation and penetration barriers, and thereby in all applications that crucially depend upon the rate of gas permeation, like gas separation for example.

Exploring the non-monotonic DNA capture behavior in a charged graphene nanopore.

Nanopore-based biomolecule detection has emerged as a promising and sought-after innovation, offering high throughput, rapidity, label-free analysis, and cost-effectiveness, with potential applications in personalized medicine. However, achieving efficient and tunable biomolecule capture into the nanopore remains a significant challenge. In this study, we employ all-atom molecular dynamics simulations to investigate the capture of double-stranded DNA (dsDNA) molecules into graphene nanopores with varying positive charges. We discover a non-monotonic relationship between the DNA capture rate and the charge of the graphene nanopore. Specifically, the capture rate initially decreases and then increases with an increase in nanopore charge. This behavior is primarily attributed to differences in the electrophoretic force, rather than the influence of electroosmosis or counterions. Furthermore, we also observe this non-monotonic trend in various ionic solutions, but not in ionless solutions. Our findings shed light on the design of novel DNA sequencing devices, offering valuable insights into enhancing biomolecule capture rates in nanopore-based sensing platforms.

The validity of the continuum modeling limit in a single pore flows to the molecular scale.

The discrete characteristics of molecules become dominant in the molecular regime when the surface-to-volume ratio becomes very high. Using the well-established continuum approach is questionable due to this dominant behavior. Due to the lack of perfect modeling of such a small-scale system, the experimentalist must rely on the trial and error method. Here we analyze the water transport mechanism through a nanoporous graphene membrane at the molecular level by adopting the classical molecular dynamics (MD) simulation. The results for SPC/E water molecules were compared with those obtained for liquid argon atoms and continuum Sampson's equation predictions. We find that the effect of local variants such as density layering, interatomic forces, slip velocity, and geometric boundary conditions become exponentially dominant with decreasing nanopore size. Consequently, the continuum assumptions break down at 1.5 nm pore diameter due to neglecting the dominant local properties.

Fabrication of 1-octane sulphonic acid modified nanoporous graphene with tuned hydrophilicity for decontamination of industrial wastewater from organic and inorganic contaminants.

This research work is based on the fabrication of a graphene oxide-based composite (GOBC) to remove the maximum number of contaminants from different industrial effluents. The GO was first intercalated with 1-octanesulphonic acid sodium salt and subjected to microwave irradiation to produce GOBC. Fixed-bed column tests and Jar-tests were performed for removal of the most harmful endocrine disrupting compounds (EDCs) such as bisphenol A, bisphenol S, endosulphan, beta-estradiol, dyes (methylene blue and violate) and toxic metal ions such as Pb2+, Li+, Ni2+, Co2+, Cr6+, Zn2+, Cd2+, Hg2+, Cu2+, and As5+via adsorption. The prepared material was thoroughly characterized for its unique functional and structural properties. The results obtained from Fourier transform infrared spectroscopy, Brunauer-Emmett-Teller, scanning electron microscopy, Raman spectroscopy, water contact angle and X-ray diffraction analysis confirmed the successful preparation of GOBC using the proposed intercalation/microwave method. The water contact angle results showed decreased hydrophilicity of GOBC as compared to GO as the contact angle of GOBC (77.75°) was higher than that of GO (53.98°). The effects of main column parameters such as bed height, initial analyte concentration and solution flow rate were investigated. The results revealed that shorter breakthrough time, and high adsorption capacity were obtained at high flow rates of 1 mL min-1, while longer breakthrough time and lower adsorption capacity were obtained at lower flow rates of 0.5 mL min-1. The effect of bed depth on the breakthrough curve of analyte adsorption was a steep breakthrough curve; or a shorter breakthrough time occurring at lower bed height. The adsorption data obeyed the Yoon-Nelson and Thomas models very well. The adsorption capacity for BPA, BPS, endosulphan, beta-estradiol, methylene blue and violate was found to be 307, 305, 260, 290, 230 and 195 mg g-1, respectively. The adsorption capacity of GOBC for toxic metal ions such as Pb2+, Li+, Ni2+, Co2+, Cr6+, Zn2+, Cd2+, Hg2+, Cu2+, and As5+ was found to be 156, 136, 126, 124, 118, 114, 82, 82, 72 and 72 mg g-1, respectively with excellent kinetics. The adsorption data obtained using Jar-tests revealed that GOBC obeys a Langmuir isotherm and a pseudo second order kinetics model. The analysis of industrial wastewater samples showed good removal efficiency of GOBC.

Low-frequency flicker noise in stochastic ionic transport across atomically thin graphene nanopores

Low-frequency flicker noise in stochastic ionic transport across atomically thin graphene nanopores