Graphene oxide membranes-partially oxidized, stacked sheets of graphene-can provide ultrathin, high-flux and energy-efficient membranes for precise ionic and molecular sieving in aqueous solution. These materials have shown potential in a variety of applications, including water desalination and purification, gas and ion separation, biosensors, proton conductors, lithium-based batteries and super-capacitors. Unlike the pores of carbon nanotube membranes, which have fixed sizes, the pores of graphene oxide membranes-that is, the interlayer spacing between graphene oxide sheets (a sheet is a single flake inside the membrane)-are of variable size. Furthermore, it is difficult to reduce the interlayer spacing sufficiently to exclude small ions and to maintain this spacing against the tendency of graphene oxide membranes to swell when immersed in aqueous solution. These challenges hinder the potential ion filtration applications of graphene oxide membranes. Here we demonstrate cationic control of the interlayer spacing of graphene oxide membranes with ångström precision using K, Na, Ca, Li or Mg ions. Moreover, membrane spacings controlled by one type of cation can efficiently and selectively exclude other cations that have larger hydrated volumes. First-principles calculations and ultraviolet absorption spectroscopy reveal that the location of the most stable cation adsorption is where oxide groups and aromatic rings coexist. Previous density functional theory computations show that other cations (Fe, Co, Cu, Cd, Cr and Pb) should have a much stronger cation-π interaction with the graphene sheet than Na has, suggesting that other ions could be used to produce a wider range of interlayer spacings.
Graphene is a well-known two-dimensional material that exhibits preeminent electrical, mechanical and thermal properties owing to its unique one-atom-thick structure. Graphene and its derivatives (e.g., graphene oxide) have become emerging nano-building blocks for separation membranes featuring distinct laminar structures and tunable physicochemical properties. Extraordinary molecular separation properties for purifying water and gases have been demonstrated by graphene-based membranes, which have attracted a huge surge of interest during the past few years. This tutorial review aims to present the latest groundbreaking advances in both the theoretical and experimental chemical science and engineering of graphene-based membranes, including their design, fabrication and application. Special attention will be given to the progresses in processing graphene and its derivatives into separation membranes with three distinct forms: a porous graphene layer, assembled graphene laminates and graphene-based composites. Moreover, critical views on separation mechanisms within graphene-based membranes will be provided based on discussing the effect of inter-layer nanochannels, defects/pores and functional groups on molecular transport. Furthermore, the separation performance of graphene-based membranes applied in pressure filtration, pervaporation and gas separation will be summarized. This article is expected to provide a compact source of relevant and timely information and will be of great interest to all chemists, physicists, materials scientists, engineers and students entering or already working in the field of graphene-based membranes and functional films.
Membrane-based separations can improve energy efficiency and reduce the environmental impacts associated with traditional approaches. Nevertheless, many challenges must be overcome to design membranes that can replace conventional gas separation processes. Here, we report on the incorporation of engineered submicrometre-sized metal-organic framework (MOF) crystals into polymers to form hybrid materials that successfully translate the excellent molecular sieving properties of face-centred cubic (fcu)-MOFs into the resultant membranes. We demonstrate, simultaneously, exceptionally enhanced separation performance in hybrid membranes for two challenging and economically important applications: the removal of CO and HS from natural gas and the separation of butane isomers. Notably, the membrane molecular sieving properties demonstrate that the deliberately regulated and contracted MOF pore-aperture size can discriminate between molecular pairs. The improved performance results from precise control of the linkers delimiting the triangular window, which is the sole entrance to the fcu-MOF pore. This rational-design hybrid approach provides a general toolbox for enhancing the transport properties of advanced membranes bearing molecular sieve fillers with sub-nanometre-sized pore-apertures.
Two-dimensional (2D) materials of atomic thickness have emerged as nano-building blocks to develop high-performance separation membranes that feature unique nanopores and/or nanochannels. These 2D-material membranes exhibit extraordinary permeation properties, opening a new avenue to ultra-fast and highly selective membranes for water and gas separation. Summarized in this Minireview are the latest ground-breaking studies in 2D-material membranes as nanosheet and laminar membranes, with a focus on starting materials, nanostructures, and transport properties. Challenges and future directions of 2D-material membranes for wide implementation are discussed briefly.
Ion transport is crucial for biological systems and membrane-based technology. Atomic-thick two-dimensional materials, especially graphene oxide (GO), have emerged as ideal building blocks for developing synthetic membranes for ion transport. However, the exclusion of small ions in a pressured filtration process remains a challenge for GO membranes. Here we report manipulation of membrane surface charge to control ion transport through GO membranes. The highly charged GO membrane surface repels high-valent co-ions owing to its high interaction energy barrier while concomitantly restraining permeation of electrostatically attracted low-valent counter-ions based on balancing overall solution charge. The deliberately regulated surface-charged GO membranes demonstrate remarkable enhancement of ion rejection with intrinsically high water permeance that exceeds the performance limits of state-of-the-art nanofiltration membranes. This facile and scalable surface charge control approach opens opportunities in selective ion transport for the fields of water transport, biomimetic ion channels and biosensors, ion batteries and energy conversions.
A graphene oxide (GO) membrane is supported on a ceramic hollow fiber prepared by a vacuum suction method. This GO membrane exhibited excellent water permeation for dimethyl carbonate/water mixtures through a pervaporation process. At 25 °C and 2.6 wt % feed water content, the permeate water content reached 95.2 wt% with a high permeation flux (1702 g m(-2) h(-1)).
Two-dimensional (2D) materials with atomic thickness and extraordinary physicochemical properties exhibit unique mass transport behaviors, enabling them as emerging nanobuilding blocks for separation membranes. Engineering 2D materials into membrane with subnanometer apertures for precise molecular sieving remains a great challenge. Here, we report rational-designing external forces to precisely manipulate nanoarchitecture of graphene oxide (GO)-assembled 2D channels with interlayer height of ∼0.4 nm for fast transporting and selective sieving gases. The external forces are synergistic to direct the GO nanosheets stacking so as to realize delicate size-tailoring of in-plane slit-like pores and plane-to-plane interlayer-galleries. The 2D channels endow GO membrane with excellent molecular-sieving characteristics that offer 2-3 orders of magnitude higher H2 permeability and 3-fold enhancement in H2/CO2 selectivity compared with commercial membranes. Formation mechanism of 2D channels is proposed on the basis of the driving forces, nanostructures, and transport behaviors.
2D materials' membranes with well-defined nanochannels are promising for precise molecular separation. Herein, the design and engineering of atomically thin 2D MXene flacks into nanofilms with a thickness of 20 nm for gas separation are reported. Well-stacked pristine MXene nanofilms are proven to show outstanding molecular sieving property for H 2 preferential transport. Chemical tuning of the MXene nanochannels is also rationally designed for selective permeating CO 2 . Borate and polyethylenimine (PEI) molecules are well interlocked into MXene layers, realizing the delicate regulation of stacking behaviors and interlayer spacing of MXene nanosheets. The MXene nanofilms with either H 2 -or CO 2 -selective transport channels exhibit excellent gas separation performance beyond the limits for state-of-the-art membranes. The mechanisms within these nanoconfined MXene layers are discussed, revealing the transformation from "diffusion-controlled" to "solution-controlled" channels after chemical tuning. This work of precisely tailoring the 2D nanostructure may inspire the exploring of nanofluidics in 2D confined space with applications in many other fields like catalysis and energy conversion processes.fabrication. Hence, MXene is considered to be a novel potential candidate for developing separative 2D-material membranes. However, there are a very few reports on MXene separation membranes. Gogotsi and co-workers first reported MXene membranes for rejection of trivalent cation in solution using nonpressure diffusion. [12] A high water permeance was obtained by applying MXene stacks in the pressure-filtration process, [13] but the membrane can only rejected matters with a size larger than 2.5 nm. Very recently, Wang and co-workers [14] reported the manufacturing of MXene membranes with highly ordered nanochannel structures for high-performance separation of H 2 /CO 2 , which opens the door of applying MXene membranes for molecular separation. It is considered that rationally regulating the nanostructure of 2D channels may, thereby, enlighten the exploring of MXene materials for sub-nanoscale separation with versatile functionalities.Herein, we report the design and engineering of MXene nanofilms with tunable transport channels for gas separation. Ultrathin pristine MXene nanofilms with a thickness down to 20 nm were fabricated by horizontally aligning the exfoliated MXene nanosheets on porous substrates. Molecular sieving channels within pristine MXene nanofilm can be formed to show highly selective H 2 permeation, as shown in Figure 1. Interestingly, these MXene laminates, as functionalized by borate and amine, exhibit different stacking behaviors and tunable interlayer spacing, allowing preferential CO 2 permeation. The resulting separation performance of either H 2 -or CO 2selective MXene nanofilms is beyond the performance limits for state-of-the-art membranes.
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