Nanoporous Graphene Research Articles

Translocation of ssDNA through Charged Graphene Nanopores: Effect of the Charge Density

Translocation of ssDNA through Charged Graphene Nanopores: Effect of the Charge Density

Atomistic insights into the K+/Na+ separation across amino modified graphene nanopore: The assisting role of Cl−

K+/Na+ separation has always been considered the most challenging. We adopted molecular dynamics to compare graphene nanopores modified with positively charged amino groups and their pristine counterparts to unravel the mechanism underlying the effect of positively charged amino groups on K+/Na+ separation and evaluate the assisting effect of Cl−. Two pore diameters of approximately 1 nm were selected. Results demonstrated that nanopore modification can effectively improve the K+/Na+ selectivity, and the spatial distribution and residence time of Cl− near the nanopores indicated that modification with positively charged amino groups can induce the dynamical adsorption of Cl− around the nanopores. In the studied nanopores, the prolongation of the residence time of Cl− at the pore mouths can increase the difference between K+ and Na+ dehydration and thus can increase their transport resistance difference. The latter effect is conducive to improving the selectivity for K+. Our findings can provide useful insight for the further design of K+ separating two-dimensional materials as sensors and ion separators.

Flexible All-Carbon Nanoarchitecture Built from In Situ Formation of Nanoporous Graphene Within "Skeletal-Capillary" Carbon Nanotube Networks for Supercapacitors.

It is difficult for carbonaceous materials to combine a large specific surface area with flexibility. Here, a flexible all-carbon nanoarchitecture based on the in situ growth of nanoporous graphene within "skeletal-capillary" carbon nanotube (CNT) networks has been achieved by a chemical vapor deposition (CVD) process. Multi-path long-range conductivity is established, and the porous graphene provides a large specific surface area for charge storage. The flexibility of the films allows them to be directly used as binder-free electrodes for supercapacitors. Since the polymeric binders are saved, the supercapacitors exhibit a higher overall storage density.

Single-Atom Underpotential Deposition at Specific Sites of N-Doped Graphene for Hydrogen Evolution Reaction Electrocatalysis

Single-atom catalysts (SACs) have the advantages of good active site uniformity, high atom utilization, and high catalytic activity. However, the study of its controllable synthesis still needs to be thoroughly investigated. In this paper, we deposited Cu SAs on nanoporous N-doped graphene by underpotential deposition and further obtained a Pt SAC by a galvanic process. Electrochemical and spectroscopic analyses showed that the pyridine-like N defect sites are the specific sites for the underpotential-deposited SAs. The obtained Pt SAC exhibits a good activity in a hydrogen evolution reaction with a turnover frequency of 25.1 s−1. This work reveals the specific sites of UPD of SAs on N-doped graphene and their potential applications in HERs, which provides a new idea for the design and synthesis of SACs.

Microstructural design of crown nanopores in graphene membrane for efficient desalination process

Designing a membrane with simultaneous high water permeability and desalination rate to overcome the trade-off presents a persistent and substantial challenge. In this paper, we employed molecular dynamics simulations to design the structure of the graphene crown ether reverse osmosis membrane and elucidate the relationship between the membrane's microscopic separation mechanism and its structure-activity.The results show that the water permeability through crown graphene nanopores exceeded that of the original graphene nanopores by an order of magnitude, and hundreds of times greater than that of the traditional reverse osmosis membrane. Additionally, the water permeation in multilayer crown graphene nanopores also surpassed that in monolayer original graphene nanopores. The water permeability exceeds 46.73 L/cm2/day/Mpa with 100 % salt rejection. Furthermore, the various sizes and shapes of graphene nanopores significantly influence water permeation. Within crown graphene nanopores, a narrow pore enables superior water permeation and salt rejection compared to a circular shape, unlike original graphene nanopores. Observed from MD simulation trajectories,this highly water permeation is caused by the hydrogen bonding between crown ether graphene and water molecules. First-principle calculations further confirm that water transport in graphene crown ether is energetically more favorable than in original graphene nanopores. Our findings support crown graphene membranes as promising candidates for seawater desalination.

A First Principles Study of Lithium Adsorption in Nanoporous Graphene

Recently, nanoporous graphene has attracted great interest in the scientific community. It possesses nano-sized holes; thus, it has a highly accessible surface area for lithium adsorption for energy storage applications. Defective graphene has been extensively studied. However, the lithium adsorption mechanism of nanoporous graphene is not clearly understood yet. Here, we present theoretical investigations on the lithium-ion adsorption mechanism in nanoporous graphene. We perform ab initio electronic structure calculations based on density functional theory. Lithium adsorption in a graphene nanopore is studied and adsorption sites are determined. We also study different lithium-ion distributions in graphene nanopores to determine the best lithium–nanoporous graphene structures for lithium-ion batteries. We show that lithium ions can be adsorbed in a graphene nanopore, even in a single layer of graphene. It is also shown that adding more nanopores to multilayer nanoporous graphene can result in higher Li storage capacity for new-generation lithium-ion batteries.

How Membrane Flexibility Impacts Permeation and Separation of Gas through Nanoporous Graphenes.

In recent years, extensive research has used molecular dynamics simulations to investigate gas separation through nanoporous graphene (NPG) membranes. However, most studies have considered graphene membranes as rigid, overlooking the impact of their inherent flexibility. This study systematically quantifies the effect of graphene flexibility on gas permeation by comparing the diffusion of various gases through flexible and rigid single-layer NPG models. The results demonstrate that flexibility notably increases permeance, particularly for gases with larger molecular diameters/pore size ratios, by allowing gas molecules greater mobility within the pore. Interestingly, the effect of flexibility boils down to the expansion of the average pore size, and the detail of the membrane's vibrational dynamics is of little importance in quantifying permeance. Our work shows that accounting for flexibility in molecular models improves the alignment of simulation results with experimental data, emphasizing the importance of considering membrane flexibility in predictive models of NPG membrane performance.

Three-Supercenter Two-Electron Bonds in C16H10: Two-Dimensional Analogue of Halogen-Bridge Bonding.

Three-center two-electron bridging bonding plays a vital role in rationalizing structures and stabilities of certain molecules. Herein, the π electron rule of pyrene (C16H10) was unraveled based on a newly proposed two-dimensional (2D) superatomic-molecule theory, where the superatomic sextet rule was regarded as a π electron counting target. C16H10 can be taken as a ◊N2◊F2 superatomic molecule, where ◊N and ◊F denote 2D superatoms bearing 3π and 5π electrons, respectively. Interestingly, it represents the first 2D superatomic halogen-bridge molecule, which realizes π electronic shell-closure via two three-supercenter two-electron bridging bonds. Additionally, a N-doped nanoporous graphene with a wide band gap (1.22 eV) was designed based on C16H10, which can be considered as a periodic aggregate of 2D superatomic wires composed of 2π-◊C and bridging ◊F superatoms. This work enriches the 2D superatomic-molecule chemistry and provides a practicable bottom-up assemble approach to obtain 2D functional materials with tunable band gaps.

Permeability of gas molecules through sub-nanometer nitrogen-terminated porous graphene membranes: A DFT study

We present a systematic theoretical investigation of gas permeability through single-layer nanoporous graphene membranes with N-terminated (pyridinic and mixed pyridinic/pyrrolic) pores for He, H2, N2, O2, CO, CO2, H2O, and CH4. Our study is based on density functional theory transition-state calculations and the kinetic theory of gasses. We systematically evaluate pores of varying sizes and shapes up to 5.7 Å in diameter. According to our findings, membranes with pores in the size regime (4.5 Å - 5.0 Å) may exhibit industrially acceptable permeance to several gas molecules and advanced selectivity. Notably, we found that, among a few others, a pore with the same topological features at the pore boundary as those of the characteristic pore of g-C3N4 carbon nitride, is particularly promising. In addition, membranes with larger pores, ∼5.5 Å - 5.7 Å, can effectively separate CH4 from the other molecules. Our findings support the advanced potential of single-layer graphene membranes with nitrogen-terminated sub-nanometer pores, for gas separation applications.

A comparative study of shale oil transport behavior in graphene and kerogen nanopores with various roughness via molecular dynamics simulations

Understanding the transport behavior of molecules within nanopores is crucial in various fields, including nanofluidic, bioengineering and geophysics. To elucidate oil flow within shale organic nanopores, the simplified carbon nanopores (e.g., graphene and CNTs) and realistic kerogen nanopores have been extensively applied. The variation in pore structure models leads to divergent findings in oil flow behavior. This study employs molecular dynamics simulations to compare alkane flows within graphene and kerogen nano-slits with similar surface roughness. We observe that using graphene nanopores with ultra-smooth surfaces may introduce errors of several orders of magnitudes in flux calculations. Conversely, when accounting for similar roughness, the static characteristics and flow behaviors in graphene and kerogen slit pores are largely comparable. The relative error of flux and the flow velocity could be lower than 6% when using graphene to replace the realistic kerogen. Alkane molecules exhibit a parabolic velocity profile, with a no-slip condition adjacent to the rough surfaces. In addition, when applying the Hagen-Poiseullie equation for alkane flow in rough nanopores, Gibbs dividing surface is recommended for defining the pore radius, reducing the error of flux predicted to below 10%. Our work fulfills the gap in accessing the suitability of using graphene as a model for oil transport in shale organic nanopores, and provides valuable insights and guidance for future studies on nanofluidic in shale, including molecular simulations, nanofluidic experiment designs, and multi-scale modeling.

Synthesis and Modular Engineering of Porous Graphene Nanoarchitectures

Bottom-up nanoarchitectonics has demonstrated the capability to control structural parameters of nanomaterials with atomic precision. The surface-assisted synthesis of graphene-based one-dimensional nanostructures à la carte distinctly illustrates the power of this concept. However, despite impressive advances in the synthesis of 1D homostructures, advancing in structural complexity faces major challenges. However, despite impressive advances in the synthesis of 1D homostructures, advancing in structural complexity faces major challenges. The functionalization of edges in nanorib-bons, an effective strategy to tailor their electronic properties and chemical interactions, is a clear example. The concept of inserting the desired functional groups or dopants in the molecular precursor often fails due to their lack of stability during the reaction path. The fabrication of heterostructures is a second example, where the challenge lies on the control of the size and distribution of their com-ponents. A third one is extending the on-surface strategy to two-dimensional structures, where examples of long-range ordered nanoarchitectures are very limited.In this talk I will present different strategies that we have developed to overcome each one of this challenges. I will show introducing our method to synthesize a 2D nanoporous graphene, where the long-range order is achieved by the sequential growth of 1D building blocks and their posterior coupling [1]. I will continue presenting two modular strategies that lead to more complex nanoporous structures. The first consist on the molecular engineering of the coupling bridges. I will show an example where the introduction of phenyl groups in the bridges brings tunability of the quantum electronic coupling and the corresponding in-plane electronic anisotropy [2]. In a final example I will focus on intercalating different 1D ribbon components in periodic arrays for the formation of lateral heterostructure superlattices where the junction is defined with atomic precision [3]. One of the components being a N-doped ribbon, the heterostructure can also be seen as a nanoporous graphene sheet bearing N-doped pores.

Emerging Advances around Nanofluidic Transport and Mass Separation under Confinement in Atomically Thin Nanoporous Graphene.

Membrane separation stands as an environmentally friendly, high permeance and selectivity, low energy demand process that deserves scientific investigation and industrialization. To address intensive demand, seeking appropriate membrane materials to surpass trade-off between permeability and selectivity and improve stability is on the schedule. 2Dmaterials offer transformational opportunities and a revolutionary platform for researching membrane separation process. Especially, the atomically thin graphene with controllable porosity and structure, as well as unique properties, is widely considered as a candidate for membrane materials aiming to provide extreme stability, exponentially large selectivity combined with high permeability. Currently, it has shown promising opportunities to develop separation membranes to tackle bottlenecks of traditional membranes, and it has been of great interest for tremendously versatile applications such as separation, energy harvesting, and sensing. In this review, starting from transport mechanisms of separation, the material selection bank is narrowed down to nanoporous graphene. The study presents an enlightening overview of very recent developments in the preparation of atomically thin nanoporous graphene and correlates surface properties of such 2D nanoporous materials to their performance in critical separation applications. Finally, challenges related to modulation and manufacturing as well as potential avenues for performance improvements are also pointed out.

Do Molecules Tunnel through Nanoporous Graphene?

The molecular transport and quantum tunneling of H2 and H2O molecules through nanoporous graphene is studied using computational modeling and first-principles density functional theory. It is demonstrated that molecules with sufficiently high kinetic energies can tunnel through nanopores. It is also demonstrated that molecules can be trapped in front of a nanopore or behind it. These investigations help us learn the behavior of molecules in and around the nanopores of graphene. They also help us learn the fundamentals of molecular tunneling. We believe nanoporous graphene can play important roles for gas separation and nanofiltration.

Ab Initio Molecular Dynamics Investigation on the Permeation of Sodium and Chloride Ions Through Nanopores in Graphene and Hexagonal Boron Nitride Membranes.

Nanoporous membranes promise energy-efficient water desalination. Hexagonal boron nitride (h-BN), like graphene, exhibits outstanding physical and chemical properties, making it a promising candidate for water treatment. We employed Car-Parrinello molecular dynamics simulations to establish an accurate modeling of Na+ and Cl- permeation through hydrogen passivated nanopores in graphene and h-BN membranes. We demonstrate that ion separation works well for the h-BN system by imposing a barrier of 0.13 eV and 0.24 eV for Na+ and Cl- permeation, respectively. In contrast, for permeation of the graphene nanopore, the Cl- ion faces a minimum of energy of 0.68 eV in the nanopore plane and is prone toward blockade of the nanopore, while the Na+ ion experiences a slight minimum of 0.03 eV. Overall, the desalination performance of h-BN nanopores surpasses that of their graphene counterparts.

Controlled Synthesis of High-Aspect-Ratio Nitrogen-Doped Nanoporous Graphene Fibers for Stable Lithium–Sulfur Batteries

Controlled Synthesis of High-Aspect-Ratio Nitrogen-Doped Nanoporous Graphene Fibers for Stable Lithium–Sulfur Batteries

Alkali Metals Adsorbed on Nanoporous Graphene: Charge Transfer and Metallic Phase

Alkali Metals Adsorbed on Nanoporous Graphene: Charge Transfer and Metallic Phase

High-energy heavy ions as a tool for production of nanoporous graphene

Single-layered supported graphene sheets were irradiated by iodine, copper, silicon, and oxygen ions in the MeV energy range. The selected ion beams cover a wide range of nuclear and electronic stopping powers. Raman spectroscopy used for the analysis of irradiated graphene samples reveals similar, nanometer-sized, pores due to the ion impacts, but with varying probability of their formation. We observed an inverse relationship between ion velocity and the size of the nanopores. Also, we observed damage accumulation is influenced by electronic stopping in all cases when electronic stopping is greater than nuclear stopping by two orders of magnitude. The systematic investigation presented in this work enables custom-made production of nanoporous graphene using high-energy heavy ion beams.

A Reverse Nonequilibrium Molecular Dynamics Algorithm for Coupled Mass and Heat Transport in Mixtures.

We present a new method for introducing stable nonequilibrium concentration gradients in molecular dynamics simulations of mixtures. This method extends earlier reverse nonequilibrium molecular dynamics (RNEMD) methods, which use kinetic energy scaling moves to create temperature or velocity gradients. In the new scaled particle flux (SPF-RNEMD) algorithm, energies and forces are computed simultaneously for a molecule existing in two nonadjacent regions of a simulation box, and the system evolves under a linear combination of these interactions. A continuously increasing particle scaling variable is responsible for the migration of the molecule between the regions as the simulation progresses, allowing for simulations under an applied particle flux. To test the method, we investigate diffusivity in mixtures of identical but distinguishable particles and in a simple mixture of multiple Lennard-Jones particles. The resulting concentration gradients provide Fick diffusion constants for mixtures. We also discuss using the new method to obtain coupled transport properties using simultaneous particle and thermal fluxes to compute the temperature dependence of the diffusion coefficient and activation energies for diffusion from a single simulation. Lastly, we demonstrate the use of this new method in interfacial systems by computing the diffusive permeability of a molecular fluid moving through a nanoporous graphene membrane.

Exploring the potential of nanoporous amorphous graphene as a reverse osmosis membrane: Insights from molecular dynamics simulations

Recently, it has been confirmed that using two-dimensional nanoporous materials as a membrane in the desalination process could be one of the future solutions to freshwater access issues. We simulated the reverse osmosis desalination process using molecular dynamics simulation (MD) to analyze the efficiency of nanoporous amorphous graphene (NPAG) to filtrate Na and Cl ions from saltwater. The findings of filtration through NPAG indicate that amorphous graphene membrane performance is lower than that of crystalline graphene, which has a higher permeability compared to standard RO membranes. The calculated ion rejection of NPAG is lower than 97% for the majority of configurations investigated.

Aromatic Rules of C22H122+/2•/2-: Flexibility in Electronic Structures of 2D Superatomic Molecules.

Triangulene (C22H122•), a nonclassic non-Kekulé polycyclic aromatic hydrocarbon, is identified to be aromatic by structural and magnetic criteria. However, its aromatic origin remains confusing. Herein, the aromatic rules of C22H122• and its two charged counterparts C22H122+/2- were investigated on the basis of a recently developed two-dimensional (2D) superatomic-molecule theory. [C22H12]2+/2•/2- exhibit obvious local aromatic characters and can be regarded as [◊N3◊O3]+, [◊N3◊O3]-, and ◊N3◊F3 superatomic molecules, respectively, where ◊N, ◊O, and ◊F denote 2D superatoms bearing 3π, 4π, and 5π electrons. [C22H12]2+/2- realize electronic shell closure via superatomic lone pairs and covalent bonds, mimicking simple molecules, whereas the α-π and β-π electrons in C22H122• follow the superatomic bonding patterns of C22H122- and C22H122+, respectively. Furthermore, based on the local character in 2D superatomic molecules, a doped nanoporous graphene, namely, C9N12B monolayer, was predicted. The material possesses excellent dynamical and thermodynamical stability, as well as a wide band gap of 2.77 eV, positioning it as a promising 2D material for future electronic applications.