In this paper, we present novel semi-permeable graphene-based membranes. Composite filters were designed and fabricated on polysulfone porous scaffolding using combinations of polycrystalline large-area High Strength Metallurgical Graphene (HSMG®), graphene oxide, hydrazine and an in-situ interfacial polymerized polyamide. The naturally occurring defects in HSMG® (which were tenths of a nanometer) were the clue in fabricating a filtering membrane. The performance of graphene membranes was evaluated in forward osmosis test. The prepared composites were proved to be semi-permeable membranes with great ions blocking efficiency (over 95%) and water flux only one order of magnitude lower than the commercial reverse osmosis membranes. The experiments’ results demonstrated that the solutions proposed in this work indicate that graphene-based membranes can be used in water treatment technology.

Graphene transfer onto ceramics, like Si/SiO₂, is well-developed and described in the literature. However, it is problematic for other ceramic materials (e.g., Al₂O₃ and ZrO₂), especially porous ones. In this case, it is mainly due to poor adhesion to the substrate, resulting in strong degradation of the graphene. For these reasons, the research topic of this study was undertaken. This article presents research on the development of the methodology of graphene transfer onto ceramic Al₂O₃ surfaces. Polycrystalline graphene chemical vapour deposition (CVD) monolayer and quasimonocrystalline high-strength metallurgical graphene (HSMG^®) synthesised on liquid copper were used. When developing the transfer methodology, the focus was on solving the problem of graphene adhesion to the surface of this type of ceramic, and thus reducing the degree of graphene deterioration at the stage of producing a ceramic–graphene composite, which stands in the way of its practical use. Plasma and chemical ceramic surface modification were applied to change its hydrophobicity, and thus to improve the adhesion between the graphene and ceramic. The modification included the use of dielectric barrier discharge (DBD) plasma, oxygen plasma (RF PACVD method - Radio Frequency Plasma Assisted Chemical Vapour Deposition), and hydrofluoric acid treatment. Changes in surface properties caused by the modifications were determined by measuring the contact angle and (in the case of chemical modification) measuring the degree of surface development. The effectiveness of the applied surface preparation methodology was evaluated based on the damage degree of CVD and HSMG^® graphene layer transferred onto modified Al₂O₃ using optical microscopy and Raman spectroscopy. The best average I_D/I_G ratio for the transferred HSMG^® graphene was obtained after oxygen plasma modification (0.63 ± 0.18) and for CVD, graphene DBD plasma was the most appropriate method (0.17 ± 0.09). The total area of graphene defects after transfer to Al₂O₃ was the smallest for HSMG^® graphene after modification with O₂ plasma (0.251 mm²/cm²), and for CVD graphene after surface modification with DBD plasma (0.083 mm²/cm²).

Graphene has been considered as a material that may overcome the limitations of polymer semi-permeable membranes in water treatment technology. However, monolayer graphene still suffers from defects that cause leakage. Here, we report a method of sealing defects in graphene transferred onto porous polymer substrate via reduced graphene oxide (rGO). The influence of various reducing agents (e.g., vitamin C, hydrazine) on the properties of rGO was investigated by SEM, Raman, FTIR, and XRD. Subsequently, membranes based on graphene/reduced graphene oxide were tested in a forward osmosis system using sodium chloride (NaCl). The effect of the effectiveness of the reduction of graphene oxide, the type and number of attached groups, the change in the distance between the rGO flakes, and the structure of this material were examined in terms of filtration efficiency. As a result, semi-permeable centimetre-scale membranes with ion blocking efficiency of up to 90% and water flux of 20 mL h⁻¹ m⁻² bar⁻¹ were proposed.

Monolayer graphene growth on liquid copper (Cu) has attracted attention due to advantages of a flat/smooth catalytic growth surface, high synthesis temperature (>1080 °C) as well as the possibility of forming graphene domains that are mobile on the liquid Cu with potential to minimize grain boundary defects and self-assemble into a continuous monolayer film. However, the quality of monolayer graphene grown on liquid copper and its suitability for size-selective ionic/molecular membrane separations has not been evaluated/studied. Here, we probe the quality of monolayer graphene grown on liquid Cu (via a metallurgical process, HSMG^®) using Scanning Electron Microscope (SEM), High-resolution transmission electron microscope (HR-TEM), Raman spectroscopy and report on a facile approach to assess intrinsic sub-nanometer to nanometer-scale defects over centimeter-scale areas. We demonstrate high transfer yields of monolayer graphene (>93% coverage) from the growth substrate to polyimide track etched membrane (PITEM, pore diameter ∼200 nm) supports to form centimeter-scale atomically thin membranes. Next, we use pressure-driven transport of ethanol to probe defects > 60 nm and diffusion-driven transport of analytes (KCl ∼0.66 nm, L-Tryptophan ∼0.7–0.9 nm, Vitamin B12 ∼1–1.5 nm and Lysozyme ∼3.8–4 nm) to probe nanoscale and sub-nanometer scale defects. Diffusive transport confirms the presence of intrinsic sub-nanometer to nanometer scale defects in monolayer graphene grown on liquid Cu are no less than that in high-quality graphene synthesized via chemical vapor deposition (CVD) on solid Cu. Our work not only benchmarks quality of graphene grown on liquid copper for membrane applications but also provides fundamental insights into the origin of intrinsic defects in large-area graphene synthesized via bottom-up processes for membrane applications.

Electrodialysis (ED) and electrodeionization (EDI) are the new methods that are being used in water desalination processes. Reliable, electrochemically stable and efficient electrodes are the crucial components of the ED/EDI electrodialysers. The article proposes a new material for electrodes in electromembrane desalination systems. Graphene composite electrodes were created by bonding carbon fibres with epoxy resin and then coated with a layer of nanostructured, reduced graphene oxide. The graphene electrode material underwent electrochemical characterization by cyclic voltammetry, electrochemical impedance spectroscopy and potentiostatic polarization techniques. FTIR and Raman spectroscopy were used to determine the material’s chemical structure. The change in the surface morphology and elemental composition of the electrodes after fabrication and exploitation of the composite was studied by SEM and EDS. The electrodes were used successfully in multi-electrode electrodialysis devices, resulting in a desalination rate of over 90%. The electrodes were proven to be functional and durable. It was also confirmed that the oxidation/reduction phenomena on the electrode surfaces were fully reversible after changing their polarization, which was used cyclically to clean the electrodialyser. The parameters obtained indicate that this material can also be successfully used in other electrode processes. Graphical

The development of new graphene-based materials necessitates the application of suitable material imaging techniques, especially for the identification of defects in the graphene structure and its continuity. For this purpose, it is natural to use one of the main properties of graphene—electrical conductivity. In this work, we prepare a 9 cm² large-area monolayer graphene membrane on porous scaffolding sealed with either GO or rGO. Then, we use electrostatic force microscopy (EFM) AFM mode along with SE and AEE SEM modes to characterize the as-prepared graphene membranes thoroughly. The combination of SEM-AEE and AFM-EFM techniques not only assesses the quality of graphene itself but also characterizes the selectivity and effectiveness of masking graphene layer defects by applying GO or rGO. This makes these methods valuable in optimizing the production of advanced graphene nanocomposites such as semipermeable membranes.