Intercalation Of Molecules Research Articles

Surface chemistry engineering and the applications of MXenes

MXenes have captured extensive attention in various fields by virtue of unique hydrophilicity, high conductivity and tunable surface terminations. In this review, the state-of-the-art progresses of designing functional MXenes have been summarized. Firstly, the synthesis methods of MXenes are summarized and classified into HF etching, in-situ HF etching and fluoride-free etching approaches based on the effect on the surface chemistry of MXenes. Secondly, the factors that affect the surface termination groups are discussed, including synthesis methods, heat treatment temperature and atmosphere. Thirdly, this review gives an overview of the synthetic routes of functional MXenes including termination modification by synthesis methods and heat treatment, heteroatom (N, S, or P) doping, cation and organic molecule intercalation and hybridization with polymer, which inhibit restacking and increase active sites for intrinsically enhancing the inherent physical and chemical properties of MXenes. Finally, the applications with respect to energy storage and conversion, catalysis, sensors, electromagnetic interference shielding and microwave absorption of functional MXenes are introduced. Additionally, the critical challenges and development prospects of functional MXenes are also highlighted.

Effect of water intercalation into tungsten trioxide structure (WO3·xH2O) (x = 0,1,2): Correlation between structure and photocatalytic performances

Tungsten oxide (WO3) is a potential photoanode material for water oxidation, however, its employment is still restricted by its limited light absorption (Eg ∼ 2.75 eV). A particular interest was devoted to tuning its electronic structure and optical bandgap in order to enhance its photocatalytic performance in hydrogen production as well as in advanced oxidation process. One of the promising alternatives for the enhancement of these photocatalytic performances, is the introduction of guest molecules into the tungsten oxide structure. In this paper, the photocatalytic performances of tungsten trioxide were highly improved by the intercalation of water into its structure. The intercalated compounds of chemical formula WO3·xH2O were prepared and characterized by TGA-DSC, PXRD, FT-IR, Raman spectroscopy, SEM-EDS and XPS. The structures of intercalated materials were refined using Rietveld method and the electronic proprieties including bandgap energy, CB and VB edges were estimated using UV–visible reflectance spectroscopy. The obtained results show that the intercalation of water molecules into tungsten oxide structure reduces the gap energy of the WO3 (2.4 eV) to 2.16 eV for WO3∙H2O and to 2.31 eV for WO3∙2H2O. The photocatalytic efficiency of the obtained materials was studied through oxygen evolution reaction tests in the presence of an electron acceptor (Ag+) and the oxidative photodegradation of the orange G dye pollutant. We found that intercalated samples exhibit the highest efficiencies compared with anhydrous samples. These findings are correlated with the increase in the average W-O-W tilt angle in WO3∙2H2O and WO3∙H2O compared to that of WO3. This improvement in the tilt angle induces the shrinkage of the energy bandgap and increases the photocatalytic performance. Furthermore, the stability of the investigated materials was studied as a function of pH, the results reveal that the intercalation of water molecules is beneficial for the chemical stability of the hydrated tungsten oxides. These findings shed light on new alternatives for band-gap engineering and improvement of materials stability through intercalation with water molecules.

Photophysics of Conjugated Oligoelectrolytes Relevant to Two‐Photon Fluorescence‐Lifetime Imaging Microscopy

AbstractConjugated oligoelectrolytes (COEs) comprise a class of cell‐membrane intercalating molecules that serve as effective optical reporters. However, little is known about the photophysical properties of COEs in biological environments such as buffers, cell membranes, and intracellular organelles, which is critical to optimize performance. Herein, how COE self‐assembly depends on the dielectric environment (polarity and ion content) is explored based on the representative molecule 6‐ring phenylenevinylene (PV) conjugated oligoelectrolyte (COE‐S6), and its optical properties within mammalian cells are subsequently studied. Two‐photon fluorescence lifetime imaging microscopy (FLIM), confocal laser scanning microscopy, and optical properties in solutions are brought together to obtain information about the location, accumulation, and characteristics of the local surroundings. FLIM imaging lifetime phasor plots, decays, and fluorescence spectra on stained mammalian cells provide evidence of successful COE‐S6 internalization via endocytosis. The fluorescence lifetime of COE‐S6 is identical when in A549 mammalian cells and in giant unilamellar vesicle model membranes, thereby providing a correlation between living system and artificial constructs.

Development of an Innovative Colorimetric DNA Biosensor Based on Sugar Measurement.

The development of biosensors for target detection plays a crucial role in advancing various fields of bioscience. This work presents the development of a genosensor that exploits the colorimetric phenol-sulfuric acid sugar reaction for the detection of DNA, and RNA as specific targets, and DNA intercalator molecules. The biosensor combines simplicity and reliability to create a novel bioassay for accurate and rapid analysis. A 96-well microplate based on a polystyrene polymer was used as the platform for an unmodified capture DNA immobilization via a silanization process and with (3-Aminopropyl) triethoxysilane (APTES). After that, a hybridization step was carried out to catch the target molecule, followed by adding phenol and sulfuric acid to quantify the amount of DNA or RNA sugar backbone. This reaction generated a yellow-orange color on the wells measured at 490 nm, which was proportional to the target concentration. Under the optimum conditions, a calibration curve was obtained for each target. The developed biosensor demonstrated high sensitivity, good selectivity, and linear response over a wide concentration range for DNA and RNA targets. Additionally, the biosensor was successfully employed for the detection of DNA intercalator agents that inhibited the hybridization of DNA complementary to the immobilized capture DNA. The developed biosensor offers a potential tool for sensitive and selective detection in various applications, including virus diagnosis, genetic analysis, pathogenic bacteria monitoring, and drug discovery.

Ionic Liquid/Na-Bentonite/Microcrystalline Cellulose Ionogels as Conductive Multifunctional Materials

For the synthesis of ionogels containing microcrystalline cellulose (MCC) and Na-bentonite (Na-Bent), ionic liquid (IL) 1-butyl-3-methylimidazolium acetate was used as an MCC solvent. Characterization and research of the physicochemical properties of the synthesized materials were carried out using methods such as SEM, WAXS, thermal analysis, FTIR, conductometry, and viscometry. WAXS analysis showed an increase in the interlayer distance of Na-bentonite in composites due to the intercalation of IL molecules. Based on the data on the characteristic temperatures of thermal degradation, enhanced thermal stability of triple IL/Na-Bent/MCC ionogels was revealed compared to that for cellulose-free systems. It was found that the electrical conductivity of both triple IL/Na-Bent/MCC and binary IL/MCC ionogels was non-monotonous. The data obtained can be used in the formation of multifunctional coatings with enhanced thermal stability.

Confined intercalating sulfonated graphene quantum dots into GO laminates for fast alkali recovery

Graphene oxide (GO) membranes with uniform sub-nanometer interlayer channels have shown great promise in the ion sieving field. However, the lack of ion-transporting sites on the GO nanosheets usually leads to inferior ion permeation and selectivity. Although the intercalation of molecules with ionic groups into GO laminates is easily achieved to incorporate ion exchange sites, this approach inevitably enlarges the interlayer spacing, reducing the ionic sieving capacity. Thus, current methods are limited in breaking the permeation and selectivity “trade-off”. Herein, we report a confined intercalation strategy to inject ample sulfonic acid groups into GO laminates using sulfonated graphene quantum dots (SGQD) as intercalators. SGQD with abundant ion exchange sites assembles on the sp2 domains of GO via π-π interactions and confers the GO membranes with continuous ion conduction pathways. Meanwhile, benefiting from the ultra-small size SGQD as well as its sheet morphology, it can well accommodate in the GO laminates. This strategy fulfills the incorporation of ionic sites without expanding channel width and destructing the two-dimensional (2D) regularity for GO laminates, resulting in simultaneous improvements in ion permeability and selectivity. Correspondingly, the resulting membranes show synergistically improving OH- dialysis coefficients of 3.5 × 10−3-8.2 × 10−3 m h−1 and OH-/WO42- separation factors of 56–116 compared with the GO membrane (0.9 × 10−3 m h−1 and 8.4) for separating simulated NaOH/Na2WO4 alkaline effluents. We believe the confined intercalating regulation can act as a versatile and fine way to modify 2D membranes for intensifying ion separation.

Rheology Engineering for Dry-Spinning Robust N-Doped MXene Sediment Fibers toward Efficient Charge Storage.

MXene nanosheets are believed to be an ideal candidate for fabricating fiber supercapacitors (FSCs) due to their metallic conductivity and superior volumetric capacitance, while challenges remain in continuously collecting bare MXene fibers (MFs) via the commonly used wet-spinning technique due to the intercalation of water molecules and a weak interaction between Ti3 C2 TX nanosheets in aqueous coagulation bath that ultimately leads to a loosely packed structure. To address this issue, for the first time, a dry-spinning strategy is proposed by engineering the rheological behavior of Ti3 C2 TX sediment and extruding the highly viscose stock directly through a spinneret followed by a solvent evaperation induced solidification. The dry-spun Ti3 C2 TX fibers show an optimal conductivity of 2295 S cm-1 , a tensile strength of 64MPa and a specific capacitance of 948 F cm-3 . Nitrogen (N) doping further improves the capacitance of MFs to 1302 F cm-3 without compromising their mechanical and electrical properties. Moreover, the FSC based on N-doped MFs exhibits a high volumetric capacitance of 293 F cm-3 , good stability over 10000 cycles, excellent flexibility upon bending-unbending, superior energy/power densities and anti-self-discharging property. The excellent electrochemical and mechanical properties endow the dry-spun MFs great potential for future applications in wearable electronics.

Nicotine–magnesium aluminum silicate complexes processed by blending: Characterization for usage as drug carriers in mucoadhesive buccal discs

Complexation of nicotine (NCT) and magnesium aluminum silicate (MAS) has been formed in the dispersions that required multiple preparation steps. In this study, physical blending was used to produce NCT–MAS complexes. NCT, a free-base liquid state form, was adsorbed onto the MAS granules, where the diffusion and intercalation of NCT molecules into the MAS silicate layers occurred. These processes required a minimum of the 7-d-resting period to reach NCT complete distribution. FTIR, XRD, and 29Si NMR suggest that NCT could interact with MAS via hydrogen bonding, water bridging, and ionic electrostatic force. The 12 % NCT–MAS complexes enabled a sustained release of NCT, after a 2-min burst, in pH 6 phosphate buffer through a particle diffusion-controlled mechanism. Buccal discs formulated with NCT–MAS complexes and sodium alginate (SA) as drug carriers and matrix former could control NCT released through drug diffusion and swelling-controlled mechanisms. NCT release and membrane permeation increased with increasing NCT–MAS complexes or decreasing SA concentration. All NCT–MAS-containing buccal discs exhibited mucoadhesive properties related to the swelling characteristics of SA and MAS. Conclusively, NCT–MAS complexes can be produced through an uncomplicated single-step blending process, and the complexes obtained presented a potential to serve as drug carriers in buccal matrix formulations.

Anomalously enhanced subcooled flow boiling in superhydrophobic graphene-nanoplatelets-coated microchannels

In boiling heat transfer, superhydrophobic surface is deemed to reduce the critical heat flux (CHF) due to the immediate formation of an insulating vapor film that inhibits effective heat transfer despite its smaller energy barrier for bubble nucleation than that of a superhydrophilic surface. Here, a subcooled flow boiling investigation is carried out in a microchannel heat sink at a low mass flux condition using the superhydrophilic and superhydrophobic graphene nanoplatelets (GNPs) composite coatings. Interestingly, the flow boiling performance of the superhydrophobic GNPs-coated microchannel significantly transcends that of its superhydrophilic counterpart. By benchmarking with the performance of an uncoated microchannel, the CHF and heat transfer coefficient of the superhydrophobic GNPs-coated microchannel are enhanced up to 134% and 135%, respectively. This anomaly is ascribed to the Cassie Baxter-to-Wenzel transition on the superhydrophobic GNPs-coated surface, which is infiltrated with liquid, restricting the nucleating bubbles from expanding into a vapor film and sustaining an efficient boiling. The initial Wenzel state of the superhydrophobic GNPs surface is primarily ascribed to the rapid intercalation of water molecules via the unique graphene nanostructure. This study sheds new light on the unique wetting behavior of graphene-nanostructured surfaces in the context of microscale flow boiling heat transfer.

Electron-modulating effects of intercalating molecules in functionalized graphene oxide: Optimizing the coordination microenvironment of Ag nanoparticles for efficient catalytic A3 coupling reactions

In this paper, functionalized graphene oxide (GO) nanosheets were modified by forming benzamide (BzA) bonds using aniline with different substituents (4-tertbutylaniline, 4-nitroaniline, aniline) as intercalating molecules. Then the Ag@R-BzA/GO composite catalysts were prepared by loading Ag nanoparticles to reveal the electronic modulation of functionalized graphene oxide interfaces by aniline molecules effects with different substituents. The experimental results showed that the layer spacing of the composites obtained after intercalation with aniline whose substituent is an electron-giving group increased by about 40%. Moreover, the electron donating role of tert‑butyl regulates the charge distribution on the graphene oxide material and provides a good coordination environment for the loading of Ag nanoparticles. AgNPs are stably present in the interlayer of graphene oxide nanosheets by ligating with amide bonds and oxygen-containing functional groups to produce strong metal-carrier interactions. Ag@4‑tert-BzA/GO composites showed high catalytic activity in the A3 coupling reaction of aldehydes, alkynes and amines for the synthesis of alkynylamines(TON=19225.82). The electronic effect of the substituent groups on the intercalated molecules reported in this paper is a modulation on the molecular and atomic scale, which provides a new idea for the modulation of the microenvironment in metal-loaded catalysts.

Tunable electrical conductivity in covalent organic frameworks by intercalation of electron acceptor molecules

Covalent organic frameworks (COFs) are crystalline organic materials with high porosity. The COFs are typically electrical insulators because of their wide bandgaps and closed-shell structures despite their π–π layer stacking motif suitable for carrier conduction. Here, we report a strategy for realizing tunable electrical conductivity in COFs by intercalating redox-active guest molecules. The approach is demonstrated using COF-5 with a boronate-ester-linked two-dimensional structure and one-dimensional nanopore channels infiltrated by 7,7,8,8-tetracyanoquinododimethane (TCNQ). Successful incorporation of guest TCNQ molecules into the cavities of the COF-5 host is confirmed by vibrational and optical spectroscopies and results in the appearance of guest–host charge-transfer transitions for TCNQ-intercalated COF-5. Overall electrical conductivities are enhanced by the carrier generation induced by the charge transfer between TCNQ and COF-5 with the retained layer-stacked structures in COF-5 also contributing to the conduction pathways. The tunable electronic properties of COFs realized by the host–guest strategies established here will further promote refinement of design principles of conductive COFs and deeper understanding of the conduction mechanism while simultaneously providing opportunities for using COFs in diverse applications.

Effect of solvation shell structure on thermopower of liquid redox pairs

AbstractDeveloping redox electrolytes with high thermopower is the key to making efficient thermogalvanic batteries for harvesting low‐grade heat. This work applies molecular dynamics simulations to predict the thermopower (i.e. thermogalvanic temperature coefficient) of the redox pairs Fe(CN)63−/Fe(CN)64− and Fe3+/Fe2+, showing excellent agreement with experimental values. We showed that of the Fe3+/Fe2+ redox pair can be increased from 1.70.4 mV/K to 3.80.5 mV/K with the increased acetone to water fraction. We discovered a significant change in the variance of solvent dipole orientation between Fe3+ and Fe2+, which can serve as a microscopic indicator for large . In mixed acetone‐water solvent, of Fe3+/Fe2+ showed a rapid increase at high acetone fractions, due to the intercalation of acetone molecules into the first solvation shell of the Fe2+ at high acetone fractions. Our discovery provides insights into how solvation shell order can be engineered to develop electrolytes with high .image

Non-swelling oxidized graphene ribbon membrane for the effective separation of cesium and strontium from radioactive liquid waste

The interlayer swelling effect of graphene oxide (GO) membranes seriously hinders their applications in the precise nanofiltration, especially sieving cesium and strontium from radioactive liquid waste. Herein, a non-swelling membrane was successfully prepared via vacuum-filtering oxidized graphene ribbons (OGR), one kind of GO analogs. The unchanged interlayer spacing in OGR membrane (OGRM) were proved to originate from the unique two-section structure of OGR building blocks. Specifically, the low-defect aromatic plane in the central axis region of OGR resulted in the strong π‒π interaction, which prevented the further intercalation of water molecules at the nanoribbon edges and locked the whole lamellar architecture, hence inhibiting the peripheral expansion of OGR. By virtue of fixed nanochannels of OGRM, an ideal separation of Cs+ and Sr2+ was realized in the multicomponent acidic waste (pH ∼2.3), and the separation factors relative to UO22+ were fCs/UO2 = 6319 and fSr/UO2 = 2705, respectively. Meanwhile, OGRM showed a fast water flux of 12.10 L m−2 h−1, 15% higher than that of graphene oxide membrane (GOM). In addition to the special interlayer nanochannels, an in-depth investigation revealed that oxygenated groups also played an important role in the ion selectivity of OGRM. This preparation strategy of the non-swelling membrane is crucial to overcome the inherent paradox between the optimal selectivity and low flux, and our findings are very useful to remediate radioactive pollution and ensure water security.

Improved performance of lithium ion batteries by employment of electrolyte containing nanodiamonds and water

Commercial lithium ion batteries (LIBs) are usually required to avoid the presence of H2O, as the intercalation of H2O molecules would lead to the degradation of both electrolyte and graphite anode, resulting in irreversible failure of the batteries. In this work, we demonstrate that assisted with introducing nanodiamonds (NDs), high concentration H2O in electrolyte (higher than 3000 ppm) can improve the performances of LIBs. For the electrolyte with 5000 ppm H2O and a small amount of NDs, the long-cycle stability and superior reversible capacities of 950 mA h g−1 at 0.1 A g−1 after 100 cycles (130 mA h g−1 at 5 A g−1 after 10,000 cycles) have been realized, which are significantly improved in comparison with the case of sole H2O introduced in the electrolyte. The improvements can be attributed to the synergistic effect of NDs and H2O achieving highly conductive SEI network, enhanced ionic conductivity and separator wettability of electrolyte, mitigated erosion of graphite anode, and increased storage sites for Li+. This work provides an efficient method to not only boost the performances of LIBs but also reduce the cost of production in practical applications.

Intercalation Effects on the Dielectric Properties of PVDF/Ti3C2Tx MXene Nanocomposites.

In this study, we report the effect of intercalation of dimethyl sulfoxide (DMSO) and urea molecules into the interlayer space of Ti3C2Tx MXene on the dielectric properties of poly(vinylidene fluoride) (PVDF)/MXene polymer nanocomposites. MXenes were obtained by a simple hydrothermal method using Ti3AlC2 and a mixture of HCl and KF, and they were then intercalated with DMSO and urea molecules to improve the exfoliation of the layers. Then, nanocomposites based on a PVDF matrix loading of 5-30 wt.% MXene were fabricated by hot pressing. The powders and nanocomposites obtained were characterized by using XRD, FTIR, and SEM. The dielectric properties of the nanocomposites were studied by impedance spectroscopy in the frequency range of 102-106 Hz. As a result, the intercalation of MXene with urea molecules made it possible to increase the permittivity from 22 to 27 and to slightly decrease the dielectric loss tangent at a filler loading of 25 wt.% and a frequency of 1 kHz. The intercalation of MXene with DMSO molecules made it possible to achieve an increase in the permittivity up to 30 at a MXene loading of 25 wt.%, but the dielectric loss tangent was increased to 0.11. A discussion of the possible mechanisms of MXene intercalation influence on the dielectric properties of PVDF/Ti3C2Tx MXene nanocomposites is presented.

An Iminostilbene Functionalized Benzimidazoline for Enhanced n‐Type Solution Doping of Semiconducting Polymers for Organic Thermoelectrics

AbstractDoped organic semiconductors play a central role in the development of several innovative optoelectronic and energy harvesting applications. Currently, the realization of thermoelectric generators, which require both hole‐ and electron‐transporting materials with high electrical conductivity, is strongly hindered by the scarce availability of stable solution‐processable n‐dopants and their limited efficiency. Herein, the synthesis of 4‐(1,3‐dimethyl‐2,3‐dihydro‐1H‐benzimidazol‐2‐yl)‐dibenzazepine (IStBI), a novel derivative belonging to the well‐known family of the benzimidazoline compounds, is presented. The functionalization with the planarized and rigid iminostilbene substituent allows, without significantly affecting the compound electronic structure, an efficient intercalation of the dopant molecules inside the ordered regions of thin films of the benchmark n‐type polymer poly(N,N′‐bis‐2‐octyldodecylnaphthalene‐1,4,5,8‐bis‐dicarboximide‐2,6‐diyl‐alt‐5,5′‐2,2′‐bithiophene) P(NDI2OD‐T2). Consequently, a maximum electrical conductivity of (1.14 ± 0.13) × 10−2 S cm−1 is recorded, exceeding by one order of magnitude what previously achieved upon solution doping of the reference P(NDI2OD‐T2) with benzimidazoline derivatives. The thermoelectric power factor is also simultaneously increased. The findings confirm that tailoring of the dopant chemical structure to improve structural interactions with the host semiconductors can be employed as a successful strategy to achieve more effective n‐doping, helping to close the performance gap with p‐type materials.

Intercalation of p-Aminopyridine and p-Ethylenediamine Molecules into Orthorhombic In1.2Ga0.8S3 Single Crystals

A single crystalline layered semiconductor In1.2Ga0.8S3 phase was grown, and by intercalating p-aminopyridine (NH2-C5H4N or p-AP) molecules into this crystal, a new intercalation compound, In1.2Ga0.8S3·0.5(NH2-C5H4N), was synthesized. Further, by substituting p-AP molecules with p-ethylenediamine (NH2-CH2-CH2-NH2 or p-EDA) in this intercalation compound, another new intercalated compound-In1.2Ga0.8S3·0.5(NH2-CH2-CH2-NH2) was synthesized. It was found that the single crystallinity of the initial In1.2Ga0.8S3 samples was retained after their intercalation despite a strong deterioration in quality. The thermal peculiarities of both the intercalation and deintercalation of the title crystal were determined. Furthermore, the unit cell parameters of the intercalation compounds were determined from X-ray diffraction data (XRD). It was found that increasing the c parameter corresponded to the dimension of the intercalated molecule. In addition to the intercalation phases' experimental characterization, the lattice dynamical properties and the electronic and bonding features of the stoichiometric GaInS3 were calculated using the Density Functional Theory within the Generalized Gradient Approximations (DFT-GGA). Nine Raman-active modes were observed and identified for this compound. The electronic gap was found to be an indirect one and the topological analysis of the electron density revealed that the interlayer bonding is rather weak, thus enabling the intercalation of organic molecules.

Bound exciton luminescence and phonon sideband analysis of iodine intercalated bulk 2H-MoSe2 crystals

Temperature dependence of the luminescence spectra of MoSe2 crystals intercalated with I2 molecules has been investigated in the temperature range 11–100 K. The spectrum of luminescence, which is caused by the recombination of excitons bound on iodine molecules embedded in the van der Waals gap (vdW), consists of zero-phonon doublet at an energy less by 0.1 eV than the width of the indirect band gap of the host crystal, and its phonon replicas. The distance between the spectral lines of this A-B doublet constitutes Δ AB =5.6 meV. From the temperature dependence of the ratio of the A and B lines intensities, it was found, that the rate of radiative recombination of the exciton state B, which is responsible for the short-wavelength line B (EB = 1.0416 eV), is 76 times higher than the recombination rate of the A state (EA = .0360 eV). Based on a comparative analysis of the structure of the luminescence spectra at different temperatures and the measured Raman spectra, it is shown that the observed nine peaks of the phonon sideband are formed by only two vibrational modes with frequencies νph1 = 144 cm−1 and νph2 = 190 cm−1. The 1st frequency corresponds to the vibrational mode due to the second-order Raman process, and the 2nd – to the local vibrational mode induced by the halogen molecule embedded in the layered crystal structure. Finally, fundamental possibilities provided by the intercalation of halogen molecules in the interface of the van der Waals heterojunctions to modify their electronic properties are considered.

2D material dispersion using a synthetic whiskey: Design of experiment optimization and preliminary application in moisture detection

The present paper deals with the preparation of 2D material dispersions using a mixture of solvents that mimics whiskey. According to the Hansen’s model, we obtained the best solvent applying a design of experiment (DoE) approach to the components present in the whiskey, as reported in literature, in order to obtain a less hazardous and green solvent. The DoE approach was also applied in the exfoliation procedure, in order to maximize the exfoliation and stability of dispersions. We obtained dispersions with a stability lasting longer than nine months in the best case. After the electrical characterization, we deposited the dispersion onto an interdigitated device in order to obtain a moisture sensor. The device showed a sensitivity due to a negative response of sensing (Grotthuss mechanism). The DC characterization showed a good response in the range 50–95% in low voltage regime (up to 3 V). The impedance spectroscopy confirms this hypothesis: the evolution of the Nyquist plot when increasing the relative humidity suggests the intercalation of water molecules among the nanoparticles.

Electrochemical Opening of Impermeable Nanochannels in Laminar Graphene Membranes for Ultrafast Nanofiltration.

Reduced graphene oxide (rGO) could be theoretically used to construct highly permeable laminar membranes with nearly frictionless nanochannels for water treatment. However, their pristine (sp2 C-C) regions usually restack into impermeable channels as a result of van der Waals interactions, resulting in a much low permeance. In this study, we demonstrate that the restacked regions could be electrochemically expanded to form ultrafast water transport nanochannels by providing a low positive potential (e.g., +1.00 V vs SCE) to the rGO membrane. Experimental investigations indicate that the structural expansion is attributed to the intercalation of water molecules into the restacked regions, driven by hydrogen bond interactions between water molecules and hydroxyl groups that are electrochemically produced on edges of rGO nanosheets. The structural expansion could be promoted by weakening the graphene-OH- interactions through intermittent application of the potential. As a result of more ultrafast water transport nanochannels available, the electrochemically treated rGO membranes could have a permeance 2 orders of magnitude higher than that of the pristine one and ∼3 times higher than that of graphene oxide membranes. Because of their smaller average pore size, the rGO membranes also have a higher ionic/molecular rejection performance than graphene oxide membranes.