Ion sieving in graphene oxide membranes via cationic control of interlayer spacing.

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+, Ca2+, Li+ or Mg2+ 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 (Fe2+, Co2+, Cu2+, Cd2+, Cr2+ and Pb2+) 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.

Unexpected Self-Assembly of Nanographene Oxide Membranes upon Electron Beam Irradiation for Ultrafast Ion Sieving.

Nanographene oxide (nGO) flakes-graphene oxide with a lateral size of ≈100 nm or less-hold great promise for superior flux and energy-efficient nanofiltration membranes for desalination and precise ionic sieving owing to their unique high-density water channels with less tortuousness. However, their potential usage is currently limited by several challenges, including the tricky self-assembly of nano-sized flakes on substrates with micron-sized pores, severe swelling in aqueous solutions, and mechanical instability. Herein, the successful fabrication of a robust membrane stacked with nGO flakes on a substrate with a pore size of 0.22 µm by vacuum filtration is reported. This membrane achieved an unprecedented water permeance above 819.1 LMH bar-1, with a high rejection rate of 99.7% for multivalent metal ions. The nGO flakes prepared using an electron beam irradiation method, have uniquely pure hydroxyl groups and abundant aromatic regions. The calculations revealed the strong hydrogen bonds between two nGO flakes, which arise from hydroxyl groups, coupled with hydrophobic aromatic regions, greatly enhance the stability of stacked flakes in aqueous solutions and increase their effective lateral size. The research presents a simple yet effective approach toward the fabrication of advanced 2D nanographene membranes with superior performance for ion sieving applications.

High-Yield Synthesis of Sodium Chlorides of Unconventional Stoichiometries.

Abnormal salt crystals with unconventional stoichiometries, such as Na2 Cl, Na3 Cl, K2 Cl, and CaCl crystals that have been explored in reduced graphene oxide membranes (rGOMs) or diamond anvil cells, hold great promise in applications due to their unique electronic, magnetic, and optical properties predicted in theory. However, the low content of these crystals, only <1% in rGOM, limits their research interest and utility in applications. Here, a high-yield synthesis of 2D abnormal crystals with unconventional stoichiometries is reported, which is achieved by applying negative potential on rGOM. A more than tenfold increase in the abnormal Na2 Cl crystals is obtained using a potential of -0.6 V, resulting in an atomic content of 13.4 ± 4.7% for Na on rGOM. Direct observations by transmission electron microscopy and piezoresponse force microscopy demonstrates a unique piezoelectric behavior arising from 2D Na2 Cl crystals with square structure. The output voltage increases from 0 to ≈180 mV in the broad 0-150° bending angle regime, which meets the voltage requirement of most nanodevices in realistic applications. Density functional theory calculations reveal that the applied negative potential of the graphene surface can strengthen the effect of the Na+ -π interaction and reduce the electrostatic repulsion between cations, making more Na2 Cl crystals formed.

Quartz Crystal Microbalance Humidity Sensors Based on Structured Graphene Oxide Membranes with Magnesium Ions: Design, Mechanism and Performance.

The application of graphene oxide (GO)-based membranes combined with a quartz crystal microbalance (QCM) as a humidity sensor has attracted great interest over the past few years. Understanding the influence of the structure of the GO membrane (GOM) on the adsorption/desorption of water molecules and the transport mechanism of water molecules in the membrane is crucial for development of applications using GOM-based humidity sensors. In this paper, by investigating the effects of oxygen-containing groups, flake size and interlayer spacing on the performance of humidity sensing, it was found that humidity-sensing performance could be improved by rational membrane-structure design and the introduction of magnesium ions, which can expand the interlayer spacing. Therefore, a novel HGO&GO&Mg2+ structure prepared by uniformly doping magnesium ions into GO&HGO thin composite membranes was designed for humidity sensing from 11.3% RH to 97.3% RH. The corresponding sensor exhibits a greatly improved humidity sensitivity (~34.3 Hz/%RH) compared with the original pure GO-based QCM sensor (~4.0 Hz/%RH). In addition, the sensor exhibits rapid response/recovery times (7 s/6 s), low hysteresis (~3.2%), excellent repeatability and good stability. This research is conducive to understanding the mechanism of GOM-based humidity sensors. Owing to its good humidity-sensing properties, the HGO&GO&Mg2+ membrane-based QCM humidity sensor is a good candidate for humidity sensing.

Graphitic-like Hexagonal Phase of Alkali Halides in Quasi-Two-Dimensional Confined Space under Ambient Conditions.

The discovery of specific matter phases with abnormal physical properties in low-dimensional systems and/or on particular substrates, such as the hexagonal phase of ice and two-dimensional (2D) CaCl with an abnormal valence state, continuously reveals more fundamental mechanisms of the nature. Alkali halides, represented by NaCl, are one of the most common compounds and usually thought to be well-understood. In the past decades, many theoretical studies suggested the existence of one particular phase, that is, the graphitic-like hexagonal phase of alkali halides at high pressure or in low-dimension states, with the expectation of improved properties of this matter phase but lacking experimental evidence due to severe technical challenges. Here, by optimized cryo-electron microscopy, we report the direct atomic-resolution observation and in situ characterization of the prevalent and stable graphitic-like alkali halide hexagonal phases, which were spontaneously formed by unsaturated NaCl and LiCl solution, respectively, in the quasi-2D confined space between reduced graphene oxide layers under ambient conditions. Combined with a control experiment, density functional theory calculations, and previous theoretical studies, we believe that a delicate balance among the cation-π interaction of the solute and substrate, electrostatic interactions of anions and cations, solute-solvent interactions, and thermodynamics under confinement synergistically results in the formation of such hexagonal crystalline phases. These findings highlight the effects of the substrate and the confined space on the formation of specific matter phases and provide a universal scheme for the preparation of special graphitic-like hexagonal phases of alkali halides.

Dynamic Behavior of Biomaterials Uncovered by Cryo-electron Microscopy.

Structural biology develops rapidly with time. The static structure analysis of biomaterials is not enough to satisfy the studies of their functional mechanisms, with a huge obstacle for the dynamic process of biological complexes. The rapid development of cryo-electron microscopy (cryo-EM) technology makes it possible to observe the near-atomic resolution structures and dynamic nature of biological macromolecules, in the fields of dynamic characteristics of proteins, protein-protein interactions, molecular recognition, and structure-based design. In this review, we systematically elaborate the contribution of cryo-EM technology in the field of biomaterials such as ribosome motion, membrane protein structure and conformational space, dynamic transmission within the plasma membrane and clinical applications. We also put forward a new standpoint in the development of cryo-EM technology.

Novel 2D CaCl crystals with metallicity, room-temperature ferromagnetism, heterojunction, piezoelectricity-like property and monovalent calcium ions.

Under ambient conditions, the only known valence state of calcium ions is +2, and the corresponding crystals with calcium ions are insulating and nonferromagnetic. Here, using cryo-electron microscopy, we report direct observation of two-dimensional (2D) CaCl crystals on reduced graphene oxide (rGO) membranes, in which the calcium ions are only monovalent (i.e. +1). Remarkably, metallic rather than insulating properties are displayed by those CaCl crystals. More interestingly, room-temperature ferromagnetism, graphene-CaCl heterojunction, coexistence of piezoelectricity-like property and metallicity, as well as the distinct hydrogen storage and release capability of the CaCl crystals in rGO membranes are experimentally demonstrated. We note that such CaCl crystals are obtained by simply incubating rGO membranes in salt solutions below the saturated concentration, under ambient conditions. Theoretical studies suggest that the formation of those abnormal crystals is attributed to the strong cation-π interactions of the Ca cations with the aromatic rings in the graphene surfaces. The findings highlight the realistic potential applications of such abnormal CaCl material with unusual electronic properties in designing novel transistors and magnetic devices, hydrogen storage, catalyzers, high-performance conducting electrodes and sensors, with a size down to atomic scale.

Adsorption of Antibiotics on Graphene and Biochar in Aqueous Solutions Induced by π-π Interactions.

The use of carbon based materials on the removal of antibiotics with high concentrations has been well studied, however the effect of this removal method is not clear on the actual concentration of environments, such as the hospital wastewater, sewage treatment plants and aquaculture wastewater. In this study, experimental studies on the adsorption of 7 antibiotics in environmental concentration of aqueous solutions by carbon based materials have been observed. Three kinds of carbon materials have shown very fast adsorption to antibiotics by liquid chromatography-tandem mass spectrometry (LC-MS-MS) detection, and the highest removal efficiency of antibiotics could reach to 100% within the range of detection limit. Surprisedly, the adsorption rate of graphene with small specific surface area was stronger than other two biochar, and adsorption rate of the two biochar which have approximate specific surface and different carbonization degree, was significantly different. The key point to the present observation were the π-π interactions between aromatic rings on adsorbed substance and carbon based materials by confocal laser scanning microscope observation. Moreover, adsorption energy markedly increased with increasing number of the π rings by using the density functional theory (DFT), showing the particular importance of π-π interactions in the adsorption process.

Hexabromocyclododecane diastereoisomers in surface sediments from river drainage basins of Shanghai, China: occurrence, distribution, and mass inventory.

Concentrations of hexabromocyclododecanes (HBCDs) were determined in surface sediments of Shanghai, China. The concentrations of total HBCD diastereoisomers (ΣHBCD) ranged from 0.01 to 13.70 ng g(-1) dry weight (dw) with a mean value of 3.41 ng g(-1) dw, which was up to several orders of magnitude lower than those reported for sediments from European countries. The ΣHBCD concentrations in sediments from chemical/textile industrial or densely populated areas were generally higher than those from rural or less chemical/textile industrialized areas in Shanghai. A high proportion of α-HBCD was observed in sediment samples and was significantly higher than that of commercial HBCD products. This might be due to thermal isomerization from γ-HBCD to α-HBCD and slower degradation rate of α-HBCD compared to γ-HBCD in anaerobic conditions. The mass inventory of ΣHBCD in surface sediments of Shanghai was estimated at 164.4 kg, representing a significant source of HBCDs to the Shanghai environment. This indicates that further study on potential transfer of HBCDs from sediments to aquatic organisms and ecological risk assessments is required.

Hexabromocyclododecanes in surface sediments from Shanghai, China: spatial distribution, seasonal variation and diastereoisomer-specific profiles.

The concentrations, spatial distribution, diastereoisomer-specific profiles of hexabromocyclododecanes (HBCDs) in surface sediments from three major rivers in Shanghai as well as the seasonal variation of HBCDs were investigated. The concentrations of total HBCD diastereoisomers ranged from 0.05 to 6.87ngg(-1)dw. Significant spatial distribution of total HBCDs concentrations were observed. The mean concentration of total HBCDs followed the order of Suzhou Creek (2.00ngg(-1))>Huangpu River (1.59ngg(-1))>Yunzao Creek (0.77ngg(-1)). The concentration was a relatively low HBCDs level compared to levels measured in domestic and other parts of the world. The proportions of α-HBCD in sediment samples were generally higher than that of commercial formulations. This might be due to thermal isomerization from γ-HBCD to α-HBCD and slower degradation rate of α-HBCD compared to γ-HBCD in anaerobic conditions. The concentrations of ΣHBCD in the summer were significantly higher than those in the winter (paired t test, p<0.01). This seasonal variation could probably be attributed to a combined effect of temperature and wet deposition. Moreover, a poor and no significant correlation between ΣHBCD levels and TOC content in sediments was observed, suggesting that the spatial distributions of HBCDs were not constrained by the TOC in sediments of Shanghai.