Recent Developments in Graphene‐Based Membranes: Structure,Mass‐Transport Mechanism and Potential Applications

Significant achievements have been made on the development of next‐generation filtration and separation membranes using graphene materials, as graphene‐based membranes can afford numerous novel mass‐transport properties that are not possible in state‐of‐art commercial membranes, making them promising in areas such as membrane separation, water desalination, proton conductors, energy storage and conversion, etc. The latest developments on understanding mass transport through graphene‐based membranes, including perfect graphene lattice, nanoporous graphene and graphene oxide membranes are reviewed here in relation to their potential applications. A summary and outlook is further provided on the opportunities and challenges in this arising field. The aspects discussed may enable researchers to better understand the mass‐transport mechanism and to optimize the synthesis of graphene‐based membranes toward large‐scale production for a wide range of applications.     

Polycrystalline Advanced Microporous Framework Membranes for Efficient Separation of Small Molecules and Ions

Advanced porous framework membranes with excellent selectivity and high permeability of small molecules and ions are highly desirable for many important industrial separation applications. There has been significant progress in the fabrication of polycrystalline microporous framework membranes (PMFMs) in recent years, such as metal–organic framework and covalent organic framework membranes. These membranes possess small pore sizes, which are comparable to the kinetic diameter of small molecules and ions on the angstrom scale, very low thickness, down to tens to hundreds of nanometers, highly oriented crystalline structures, hybrid membrane structures, and specific functional groups for enhancing membrane selectivity and permeability. Recent advances in the fabrication methods of advanced PMFMs are summarized. Following this, four emerging separation applications of these advanced microporous framework membranes, including gas separation, water desalination, ion separation, and chiral separation, are highlighted and discussed in detail. Finally, a summary and some perspectives of future developments and challenges in this exciting research field are presented.     

新型无机二维材料在气体分离膜领域的研究进展

气体膜分离技术是过滤与分离工业的重要技术之一,相比于传统分离技术更加高效、节能、环保。新型无机二维材料在分离膜领域的应用,有望同时实现高选择性和高渗透率,突破商业聚合物膜渗透率和选择性相互制约的瓶颈,极大地促进高性能分离膜的发展。本文简述了膜的气体分离机制,综述了石墨烯基、过渡金属硫族化物(TMDs)和二维过渡金属碳化物/氮化物(MXene)等新型无机二维材料近年来在气体分离膜领域的研究进展,包括其设计、制造和应用,探讨了不同材料分离膜的特点、面临的挑战和发展前景。此外,本文对其他新兴二维材料——层状双氢氧化物(LDHs)、六方氮化硼(h-BN)、云母纳米片等的分离膜研究也进行了概述。最后,对新型无机二维材料在气体分离膜领域的研究方向及面临的挑战作出了评价。     

Sulfonated Graphene as Cation‐Selective Coating: A New Strategy for High‐Performance Membrane Capacitive Deionization

Membrane capacitive deionization (MCDI) featuring both high electrosorption capacity and high energy efficiency holds promise for desalination. However, the large‐scale applications of MCDI are limited greatly by the high cost of commercial ion‐exchange membranes and the interfacial resistance. Here, a new strategy for high‐performance MCDI is established using sulfonated graphene (SG) as cation‐selective coating. A continuous ultrathin SG coating via self‐assembly is formed and attached tightly onto the surface of electrospun carbon nanofibers (CNFs) by a simple yet effective dip‐coating technique, yielding SG‐CNF composites with a hydrophilic surface, high electrochemical specific capacitance, and greatly reduced interfacial charge transfer rate. These result in significantly enhanced capacitive deionization performance in terms of both electrosorption capacity and charge efficiency. The SG coating shows excellent cation selectivity for an asymmetric cell with SG–CNFs as a cathode. The new approach may pave a way to novel micro‐MCDI, i.e. novel applications of functional graphene‐based materials for high‐performance, energy‐efficient, and cost‐effective desalination.     

Microstructural Engineering and Architectural Design of Metal–Organic Framework Membranes

In the past decade, a huge development in rational design, synthesis, and application of molecular sieve membranes, which typically included zeolites, metal–organic frameworks (MOFs), and graphene oxides, has been witnessed. Owing to high flexibility in both pore apertures and functionality, MOFs in the form of membranes have offered unprecedented opportunities for energy‐efficient gas separations. Reports on the fabrication of well‐intergrown MOF membranes first appeared in 2009. Since then there has been tremendous growth in this area along with an exponential increase of MOF‐membrane‐related publications. In order to compete with other separation and purification technologies, like cryogenic distillation, pressure swing adsorption, and chemical absorption, separation performance (including permeability, selectivity, and long‐term stability) of molecular sieve membranes must be further improved in an attempt to reach an economically attractive region. Therefore, microstructural engineering and architectural design of MOF membranes at mesoscopic and microscopic levels become indispensable. This review summarizes some intriguing research that may potentially contribute to large‐scale applications of MOF membranes in the future.     

Multiscale Design of Graphyne‐Based Materials for High‐Performance Separation Membranes

By varying the number of acetylenic linkages connecting aromatic rings, a new family of atomically thin graph‐n‐yne materials can be designed and synthesized. Generating immense scientific interest due to its structural diversity and excellent physical properties, graph‐n‐yne has opened new avenues toward numerous promising engineering applications, especially for separation membranes with precise pore sizes. Having these tunable pore sizes in combination with their excellent mechanical strength to withstand high pressures, free‐standing graph‐n‐yne is theoretically posited to be an outstanding membrane material for separating or purifying mixtures of either gases or liquids, rivaling or even dramatically exceeding the capabilities of current, state‐of‐art separation membranes. Computational modeling and simulations play an integral role in the bottom‐up design and characterization of these graph‐n‐yne materials. Thus, here, the state of the art in modeling α‐, β‐, γ‐, δ‐, and 6,6,12‐graphyne nanosheets for synthesizing graph‐2‐yne materials and 3D architectures thereof is discussed. Different synthesis methods are described and a broad overview of computational characterizations of graph‐n‐yne's electrical, chemical, and thermal properties is provided. Furthermore, a series of in‐depth computational studies that delve into the specifics of graph‐n‐yne's mechanical strength and porosity, which confer superior performance for separation and desalination membranes, are reviewed.     

Ultrafiltration Membranes with Structure‐Optimized Graphene‐Oxide Coatings for Antifouling Oil/Water Separation

Fouling of ultrafiltration (UF) membranes in oil/water separation is a long‐standing issue and a major economic barrier to their use in a broad range of applications. Currently reported membranes typically show severe fouling, resulting from the strong oil adhesion on the membrane surface and/or oil penetration inside the membranes. This greatly degrades their performance and shortens service lifetime. Here, the use of graphene oxide (GO) as a novel coating material for the fabrication of fully recoverable, UF membranes with desired hierarchical surface roughness is accomplished by a facile vacuum filtration method for antifouling oil/water separation. The combination of ultrathin, “water‐locking” GO coatings with the optimized hierarchical surface roughness, provided by the inherent roughness of the porous supports and the corrugation of the GO coatings, minimizes underwater oil adhesion on the membrane surface. Cyclic membrane performance evaluation tests revealed approximately 100% membrane recovery by facile surface water flushing, establishing their excellent easy‐to‐recover capability. The novel GO functional coatings with optimized hierarchical structures may have broad applications in oil‐polluted environments.     

Reduced graphene oxide/metal oxide nanoparticles composite membranes for highly efficient molecular separation

Graphene oxide(GO) membranes play an important role in various nanofiltration applications including desalination, water purification, gas separation, and pervaporation. However, it is still very challenging to achieve both high separation efficiency and good water permeance at the same time. Here, we synthesized two kinds of GO-based composite membranes i.e. reduced GO(rGO)@MoO_2 and rGO@WO_3 by in-situ growth of metal nanoparticles on the surface of GO sheets. They show a high separation efficiency of ～100% for various organic dyes such as rhodamine B, methylene blue and evans blue, along with a water permeance over 125 Lm~(-2) h~(-1) bar~(-1). The high water permeance and rejection efficiency open up the possibility for the real applications of our GO composite membranes in water purification and wastewater treatment. Furthermore, this composite strategy can be readily extended to the fabrication of other ultrathin molecular sieving membranes for a wide range of molecular separation applications.     

MXene Materials for Designing Advanced Separation Membranes

MXenes are emerging rapidly as a new family of multifunctional nanomaterials with prospective applications rivaling that of graphenes. Herein, a timely account of the design and performance evaluation of MXene-based membranes is provided. First, the preparation and physicochemical characteristics of MXenes are outlined, with a focus on exfoliation, dispersion stability, and processability, which are crucial factors for membrane fabrication. Then, different formats of MXene-based membranes in the literature are introduced, comprising pristine or intercalated nanolaminates and polymer-based nanocomposites. Next, the major membrane processes so far pursued by MXenes are evaluated, covering gas separation, wastewater treatment, desalination, and organic solvent purification. The potential utility of MXenes in phase inversion and interfacial polymerization, as well as layer-by-layer assembly for the preparation of nanocomposite membranes, is also critically discussed. Looking forward, exploiting the high electrical conductivity and catalytic activity of certain MXenes is put into perspective for niche applications that are not easily achievable by other nanomaterials. Furthermore, the benefits of simulation/modeling approaches for designing MXene-based membranes are exemplified. Overall, critical insights are provided for materials science and membrane communities to navigate better while exploring the potential of MXenes for developing advanced separation membranes.     

Laser-induced graphene and carbon nanotubes as conductive carbon-based materials in environmental technology

Nanotechnology and nanomaterials have attracted interest due to their potential in mitigating contemporary environmental challenges, such as the stressors imposed by increased industrial and agricultural activities, and the deterioration of air, soil and water quality. In particular, advanced technologies that harness carbon-based nanomaterials are poised to emerge as tools that provide new solutions for the global water crises. These tools include, electrically conductive membrane processes, which uniquely combine a separation process with a functional surface. In this respect, laser-induced graphene (LIG) and carbon nanotubes (CNTs) are electrically conductive carbon nanomaterials that hold great utility in a multitude of environmental applications, including the development of fouling-resistant systems for desalination and water treatment, enhanced separation methods, and innovative pollutant sensing and electrocatalytic platforms. Consequently, this review article describes and compares some important recent advances in LIG- and CNT-based electroactive surfaces. The discussion of LIG as an emerging carbon material set in context with CNTs is intended to shed light on future directions and development possibilities to meet the growing global challenges in terms of water treatment applications of both materials as well as other electrically conductive carbon-based nanomaterials exhibiting exceptional performance and versatility.     

Chemically Integrated Inorganic‐Graphene Two‐Dimensional Hybrid Materials for Flexible Energy Storage Devices

State‐of‐the‐art energy storage devices are capable of delivering reasonably high energy density (lithium ion batteries) or high power density (supercapacitors). There is an increasing need for these power sources with not only superior electrochemical performance, but also exceptional flexibility. Graphene has come on to the scene and advancements are being made in integration of various electrochemically active compounds onto graphene or its derivatives so as to utilize their flexibility. Many innovative synthesis techniques have led to novel graphene‐based hybrid two‐dimensional nanostructures. Here, the chemically integrated inorganic‐graphene hybrid two‐dimensional materials and their applications for energy storage devices are examined. First, the synthesis and characterization of different kinds of inorganic‐graphene hybrid nanostructures are summarized, and then the most relevant applications of inorganic‐graphene hybrid materials in flexible energy storage devices are reviewed. The general design rules of using graphene‐based hybrid 2D materials for energy storage devices and their current limitations and future potential to advance energy storage technologies are also discussed.     

Membrane thinning for efficient CO2 capture

Abstract

Enhancing the fluxes in gas separation membranes is required for utilizing the membranes on a mass scale for CO₂ capture. Membrane thinning is one of the most promising approaches to achieve high fluxes. In addition, sophisticated molecular transport across membranes can boost gas separation performance. In this review, we attempt to summarize the current state of CO₂ separation membranes, especially from the viewpoint of thinning the selective layers and the membrane itself. The gas permeation behavior of membranes with ultimate thicknesses and their future directions are discussed.     

Cation–π Interactions in Graphene-Containing Systems for Water Treatment and Beyond

Cation–π interactions are common in nature, especially in organisms. Their profound influences in chemistry, physics, and biology have been continuously investigated since they were discovered in 1981. However, the importance of cation–π interactions in materials science, regarding carbonaceous nanomaterials, has just been realized. The interplay between cations and delocalized polarizable π electrons of graphene would bring about significant changes to the intrinsic characteristics of graphene and greatly affect the device performance based on graphene and its derivatives. Here, the cation–π interactions in graphene containing systems for water treatment applications (e.g., separation membranes, adsorbents) are highlighted. The cross-linking effects caused by cation–π interactions contribute to membrane stability and selectivity and enhanced adsorption. Their roles in dominating the performance of graphene-based structures for other specific applications are also discussed. Relevant theoretical modeling and calculations are summarized to offer an in-depth understanding of the underlying mechanisms which can help in designing more functional materials and structures. Perspectives on the potential directions that deserve effort are also presented.     

Dual‐Ion Electrochemical Deionization System with Binder‐Free Aerogel Electrodes

Desalination devices such as capacitive deionization (CDI) have been developed for many years as an approach to relief freshwater shortage. However, due to the limitation of physical adsorption capacity of CDI, the salt removal capacity is unable to reach high value. To enhance the desalination capacity effectively, battery materials are employed to fabricate a dual‐ion electrochemical deionization (DEDI) device. Herein, a binder‐free DEDI system with two free‐standing aerogel electrodes is reported. A Na₃V₂(PO₄)₃/graphene hybrid aerogel is used as sodium electrode and a AgCl/graphene hybrid aerogel is used as chloride electrode. With electric current passing through, sodium and chloride ions are released or absorbed by two aerogel electrodes. This system achieves super high desalination capacity, excellent cycling stability, and rapid desalination rate. The desalination capacity is as high as 107.5 mg g^?1 after 50 cycles with the current density of 100 mA g^?1. The outstanding desalination performance of this system shows a synergistic effect of combining battery materials with graphene for deionization and promises a new potential alternative of future desalination design.     

Synthetic Two‐Dimensional Materials: A New Paradigm of Membranes for Ultimate Separation

Microporous membranes act as selective barriers and play an important role in industrial gas separation and water purification. The permeability of such membranes is inversely proportional to their thickness. Synthetic two‐dimensional materials (2DMs), with a thickness of one to a few atoms or monomer units are ideal candidates for developing separation membranes. Here, groundbreaking advances in the design, synthesis, processing, and application of 2DMs for gas and ion separations, as well as water desalination are presented. This report describes the syntheses, structures, and mechanical properties of 2DMs. The established methods for processing 2DMs into selective permeation membranes are also discussed and the separation mechanism and their performances addressed. Current challenges and emerging research directions, which need to be addressed for developing next‐generation separation membranes, are summarized.     

Effective Separation of CO2 Using Metal-Incorporated rGO Membranes

Graphene-based materials, primarily graphene oxide (GO), have shown excellent separation and purification characteristics. Precise molecular sieving is potentially possible using graphene oxide-based membranes, if the porosity can be matched with the kinetic diameters of the gas molecules, which is possible via the tuning of graphene oxide interlayer spacing to take advantage of gas species interactions with graphene oxide channels. Here, highly effective separation of gases from their mixtures by using uniquely tailored porosity in mildly reduced graphene oxide (rGO) based membranes is reported. The gas permeation experiments, adsorption measurement, and density functional theory calculations show that this membrane preparation method allows tuning the selectivity for targeted molecules via the intercalation of specific transition metal ions. In particular, rGO membranes intercalated with Fe ions that offer ordered porosity, show excellent reproducible N₂/CO₂ selectivity of ≈97 at 110 mbar, which is an unprecedented value for graphene-based membranes. By exploring the impact of Fe intercalated rGO membranes, it is revealed that the increasing transmembrane pressure leads to a transition of N₂ diffusion mode from Maxwell–Stefan type to Knudsen type. This study will lead to new avenues for the applications of graphene for efficiently separating CO₂ from N₂ and other gases.     

Clean Transfer of Large Graphene Single Crystals for High‐Intactness Suspended Membranes and Liquid Cells

The atomically thin 2D nature of suspended graphene membranes holds promising in numerous technological applications. In particular, the outstanding transparency to electron beam endows graphene membranes great potential as a candidate for specimen support of transmission electron microscopy (TEM). However, major hurdles remain to be addressed to acquire an ultraclean, high‐intactness, and defect‐free suspended graphene membrane. Here, a polymer‐free clean transfer of sub‐centimeter‐sized graphene single crystals onto TEM grids to fabricate large‐area and high‐quality suspended graphene membranes has been achieved. Through the control of interfacial force during the transfer, the intactness of large‐area graphene membranes can be as high as 95%, prominently larger than reported values in previous works. Graphene liquid cells are readily prepared by π–π stacking two clean single‐crystal graphene TEM grids, in which atomic‐scale resolution imaging and temporal evolution of colloid Au nanoparticles are recorded. This facile and scalable production of clean and high‐quality suspended graphene membrane is promising toward their wide applications for electron and optical microscopy.     

Programmed Synthesis of Freestanding Graphene Nanomembrane Arrays

Freestanding graphene membranes are unique materials. The combination of atomically thin dimensions, remarkable mechanical robustness, and chemical stability make porous and non‐porous graphene membranes attractive for water purification and various sensing applications. Nanopores in graphene and other 2D materials have been identified as promising devices for next‐generation DNA sequencing based on readout of either transverse DNA base‐gated current or through‐pore ion current. While several ground breaking studies of graphene‐based nanopores for DNA analysis have been reported, all methods to date require a physical transfer of the graphene from its source of production onto an aperture support. The transfer process is slow and often leads to tears in the graphene that render many devices useless for nanopore measurements. In this work, we report a novel scalable approach for site‐directed fabrication of pinhole‐free graphene nanomembranes. Our approach yields high quality few‐layer graphene nanomembranes produced in less than a day using a few steps that do not involve transfer. We highlight the functionality of these graphene devices by measuring DNA translocation through electron‐beam fabricated nanopores in such membranes.     

Water desalination across nanoporous graphene

We show that nanometer-scale pores in single-layer freestanding graphene can effectively filter NaCl salt from water. Using classical molecular dynamics, we report the desalination performance of such membranes as a function of pore size, chemical functionalization, and applied pressure. Our results indicate that the membrane's ability to prevent the salt passage depends critically on pore diameter with adequately sized pores allowing for water flow while blocking ions. Further, an investigation into the role of chemical functional groups bonded to the edges of graphene pores suggests that commonly occurring hydroxyl groups can roughly double the water flux thanks to their hydrophilic character. The increase in water flux comes at the expense of less consistent salt rejection performance, which we attribute to the ability of hydroxyl functional groups to substitute for water molecules in the hydration shell of the ions. Overall, our results indicate that the water permeability of this material is several orders of magnitude higher than conventional reverse osmosis membranes, and that nanoporous graphene may have a valuable role to play for water purification.     

Nanostructured materials for water desalination

Desalination of seawater and brackish water is becoming an increasingly important means to address the scarcity of fresh water resources in the world. Decreasing the energy requirements and infrastructure costs of existing desalination technologies remains a challenge. By enabling the manipulation of matter and control of transport at nanometer length scales, the emergence of nanotechnology offers new opportunities to advance water desalination technologies. This review focuses on nanostructured materials that are directly involved in the separation of water from salt as opposed to mitigating issues such as fouling. We discuss separation mechanisms and novel transport phenomena in materials including zeolites, carbon nanotubes, and graphene with potential applications to reverse osmosis, capacitive deionization, and multi-stage flash, among others. Such nanostructured materials can potentially enable the development of next-generation desalination systems with increased efficiency and capacity.