In this study, we report a heterogeneously stacked MoS2-Graphene Oxide (GO) membrane that demonstrates enhanced resistance to restacking and swelling compared to homogeneously stacked pure MoS2 or GO membranes. The heterogeneous membrane was prepared using a mixture of MoS2 and GO suspensions with varying ratios. X-ray diffraction analysis reveals three stacking structures within the heterogeneous membrane: neighboring GO-GO, MoS2–MoS2, and MoS2-GO nanosheets. Combining XRD results and theoretical calculations, we determine that the alternately stacked MoS2-GO structure has an interlayer spacing of 0.86 ± 0.07 nm, with a free spacing of around 0.53 nm when dried. By optimizing the MoS2 to GO ratio, we can achieve a structure dominated by alternately stacked MoS2-GO nanosheets, which leads to improved filtration performances due to minimized swelling and restacking. One significant advantage of the heterogeneous MoS2-GO structure is its stability in aqueous environment. Unlike GO membranes, which can swell up to six times their original thickness, the heterogenous MoS2-GO membrane has shown minimum swelling, resulting in improved membrane selectivity. Additionally, the layer-stacked heterogeneity of the MoS2-GO structure mitigates the restacking problem inherent in pure MoS2 membranes when dried, which can lead to an irreversible loss of water permeability. In conclusion, our findings demonstrate that creating a heterogeneously stacked MoS2-GO membrane significantly improves both membrane stability and separation performances compared to homogenous pure GO or MoS2 membranes.

Ion-selective membranes are necessary components of many electrochemical systems including fuel cells, electrolyzers, redox flow batteries, and electrodialyzers. Perfluorinated sulfonated membranes (PFSMs) dominate these applications due to their excellent combination of fast ion transport, stability, and processability. However, perfluorinated cation exchange membranes (CEMs) are expensive, and their production process involves chemistry that generates toxic perfluorinated chemicals. The development of affordable, nonfluorinated membranes with a competitive combination of high ion selectivity, transport, and stability could help enable the widespread use of the technologies listed above while hastening the development of emerging electrochemical systems, including aqueous alkaline CO2 sorbent regeneration. To this end, we pursue the use of thin-film composite polyamide (PA-TFCs) membranes─those that typically find application in reverse osmosis and nanofiltration desalination─as cation-selective exchange membranes. Given their negative surface charge under neutral-to-alkaline conditions, PA-TFCs can serve as effective CEMs in these pH regimes. We prepared a series of PA-TFCs from traditional monomers (trimesoyl chloride and piperazine) and compared their thicknesses, charge densities, water transport properties, ion transport properties, and long-term stability in a high pH environment to traditional CEMs (Nafion and FKE) and commercial nanofiltration and reverse osmosis membranes. We find that some of the best-performing PA-TFC membranes have similar resistances and Na+ transference numbers compared to Nafion 117 in Na2SO4 and NaHCO3-containing solutions. This proof-of-principle study suggests that further optimization of PA-TFCs could enable cost-effective ion exchange membrane alternatives to PFSMs.

Layer-by-layer (LbL) assembly of oppositely charged materials has been widely used as an approach to make two-dimensional (2D) nanosheet-based membranes, which often involves 2D nanosheets being alternately deposited with polymer-based polyelectrolytes to obtain an electrostabilized nanosheet-polymer structure. In this study, we hypothesized that using 2D nanosheets with matching physical properties as both polyanions and polycations may result in a more ordered nanostructure with better stability than a nanosheet-polymer structure. To compare the differences between nanosheet-nanosheet vs nanosheet-polymer structures, we assembled negatively charged molybdenum disulfide nanosheets (MoS₂) with either positively charged graphene oxide (PrGO) nanosheets or positively charged polymer (PDDA). Using combined measurements by ellipsometer and quartz crystal microbalance with dissipation, we discovered that the swelling of MoS₂-PrGO in ionic solutions was 60% lower than that of MoS₂-PDDA membranes. Meanwhile, the MoS₂-PrGO membrane retained its permeability upon drying, whereas the permeability of MoS₂-PDDA decreased by 40% due to the restacking of MoS₂. Overall, the MoS₂-PrGO membrane demonstrated a better filtration performance. Additionally, our X-ray photoelectron spectroscopy results and analysis on layer density revealed a clearer transition in material composition during the LbL synthesis of MoS₂-PrGO membranes, and the X-ray diffraction pattern suggested its resemblance to an ordered, layer-stacked structure. In conclusion, the MoS₂-PrGO membrane made with nanosheets with matching size, shape, and charge density exhibited a much more aligned stacking structure, resulting in reduced membrane swelling under high salinity solutions, controlled restacking, and improved separation performance.

Membranes synthesized by stacking two-dimensional graphene oxide (GO) hold great promise for applications in organic solvent nanofiltration. However, the performance of a layer-stacked GO membrane in organic solvent nanofiltration can be significantly affected by its swelling and interlayer spacing, which have not been systematically characterized. In this study, the interlayer spacing of the layer-stacked GO membrane in different organic solvents was experimentally characterized by liquid-phase ellipsometry. To understand the swelling mechanism, the solubility parameters of GO were experimentally determined and used to mathematically predict the Hansen solubility distance between GO and solvents, which is found to be a good predictor for GO swelling and interlayer spacing. Solvents with a small solubility distance (e.g., dimethylformamide, N-methyl-2-pyrrolidone) tend to cause significant GO swelling, resulting in an interlayer spacing of up to 2.7 nm. Solvents with a solubility distance larger than 9.5 (e.g., ethanol, acetone, hexane, and toluene) only cause minor swelling and are thus able to maintain an interlayer spacing of around 1 nm. Correspondingly, GO membranes in solvents with a large solubility distance exhibit good separation performance, for example, rejection of more than 90% of the small organic dye molecules (e.g., rhodamine B and methylene blue) in ethanol and acetone. Additionally, solvents with a large solubility distance result in a high slip velocity in GO channels and thus high solvent flux through the GO membrane. In summary, the GO membrane performs better in solvents that are unlike GO, i.e., solvents with large solubility distance.

One great advantage of graphene-polyelectrolyte multilayer (GPM) membranes is their tunable structure and internal charge for improved separation performance. In this study, we synthesized GO-dominant GPM membrane with internal negatively-charged domains, polyethyleneimine (PEI)-dominant GPM membrane with internal positively-charged domains and charge-balanced dense/loose GPM membranes by simply adjusting the ionic strength and pH of the GO and PEI solutions used in layer-by-layer membrane synthesis. A combined system of quartz crystal microbalance with dissipation (QCM-D) and ellipsometry was used to analyze the mass deposition, film thickness, and layer density of the GPM membranes. The performance of the GPM membranes were compared in terms of both permeability and selectivity to determine the optimal membrane structure and synthesis strategy. One effective strategy to improve the GPM membrane permeability-selectivity tradeoff is to assemble charge-balanced dense membranes under weak electrostatic interactions. This balanced membrane exhibits the highest MgCl2 selectivity (∼86%). Another effective strategy for improved cation removal is to create PEI-dominant membranes that provide internal positively-charged barrier to enhance cation selectivity without sacrificing water permeability. These findings shine lights on the development of a systematic approach to push the boundary of permeability-selectivity tradeoff for GPM membranes.

Dehydration has been a key limiting factor for the operation of conductive hydrogels in practical application. Here, we report self-healable ionic skins that can self-regulate their internal moisture level by capturing extenral moistures via hygroscopic ion-coordinated polymer backbones through antipolyelectrolyte effect. Results show the ionic skin can maintain its mechanical and electrical functions over 16 months in the ambient environment with high stretchability (fracture stretch ∼2216 %) and conductivity (23.5 mS/cm). The moisture self-regulating capability is further demonstrated by repeated exposures to harsh environments such as 200°C heating, freezing, and vacuum drying with recovered conductivity and stretchability. Their reversible ionic and hydrogen bonds also enable self-healing feature as a sample with the fully cut-through damage can restore its conductivity after 24 h at 40 % relative humidity. Utilizing the ionic skin as a building block, self-healing flexible piezoelecret sensors have been constructed to monitor physiological signals. Together with a facile transfer-printing process, a self-powered sensing system with a self-healable supercapacitor and humidity sensor has been successfully demonstrated. These results illustrate broad-ranging possibilities for the ionic skins in applications such as energy storage, wearable sensors, and human-machine interfaces.