Reduced Graphene Oxide Membranes Research Articles

Insights into the Hydration Layer of Reduced Graphene Oxides: A Computational Stud.

Reduced graphene oxide (rGO) has emerged as a versatile material with diverse applications, particularly in aqueous environments. Understanding its interactions with water molecules is crucial for various fields, ranging from energy storage to sensing. In this study, we investigate the behavior of graphene and rGO in water, focusing on elucidating their wetting properties and the influence of oxygen-containing functional groups. Through extensive molecular dynamics simulations, we analyze the orientation and electrostatic dipole of water molecules near the rGO interface, revealing a direct correlation between rGO hydrophilicity and oxidation level. Specifically, we observe stronger hydrogen bonding networks near higher coverage rGO monolayers, indicating enhanced hydrophilicity. Furthermore, by studying water confined between rGO layers, we find uniform water transport with lateral self-diffusion coefficients comparable to bulk water, highlighting the potential of rGO membranes in various applications. Our findings provide insights into the atomic-scale interactions governing rGO-water interfaces, paving the way for the rational design of graphene-based materials for application in aqueous environments.

Genipin Nanoparticles-Doped Reduced Graphene Oxide Membranes: A Promising Solution for Arsenic Ion Removal From Wastewater

Genipin Nanoparticles-Doped Reduced Graphene Oxide Membranes: A Promising Solution for Arsenic Ion Removal From Wastewater

Rapid and efficient separation of radioactive cesium ion/other radioactive ions by reduced graphene oxide membrane

Separation of cesium ions from other radioactive ions is of great significance for recycling and utilization of radioactive sources, facilitating the management of highly radioactive liquid waste (HLW), as well as for environmental protection. We achieved a highly selective and efficient separation of binary mixtures of 137Cs/60Co, Cs+/Co2+, Cs+/Ni2+, and Cs+/Zn2+ using amino-hydrothermal reduced graphene oxide membranes. The separation factor for non-radioactive binary mixtures is up to 4290, with a water permeance of 50.8 L m−2 h−1 bar−1. The separation factor for radioactive 137Cs/60Co is 623, which is somewhat underestimated due to the detection limit of the high-purity germanium spectrometer. The rGO membranes has the high water permeance of 72.4 L m−2 h−1 bar−1, with a thickness of ∼300 nm. The rGO membrane achieved effective separation of cesium and cobalt ions over a wide range of cesium-to-cobalt ion concentration ratios, with the best results achieved at a concentration ratio of 100:1 for cesium and cobalt. In addition, the rGO membranes showed outstanding stability. The superior performance is attributed to the amino hydrothermal treatment, which reduced oxygen functional groups and directly inserted nitrogen atoms into the GO lattice, ultimately forming stable narrow nanochannels conducive to the size-sieving effect. The findings show that the rGO membranes have excellent separation performance due to their size-sieving effect, and this work has great potential for rapid and efficient treatment of radioactive liquid waste.

Efficient Ionovoltaic Energy Harvesting via Water-Induced p-n Junction in Reduced Graphene Oxide.

Water motion-induced energy harvesting has emerged as a prominent means of facilitating renewable electricity from the interaction between nanostructured materials and water over the past decade. Despite the growing interest, comprehension of the intricate solid-liquid interfacial phenomena related to solid state physics remains elusive and serves as a hindrance to enhancing energy harvesting efficiency up to the practical level. Herein, the study introduces the energy harvester by utilizing inversion on the majority charge carrier in graphene materials upon interaction with water molecules. Specifically, various metal electrode configurations are employed on reduced graphene oxide (rGO) to unravel its distinctive charge carriers that experience the inversion in semiconductor type upon water contact, and exploit this characteristic to leverage the efficacy of generated electricity. Through the strategic arrangement of the metal electrodes on rGO membrane, the open-circuit voltage (Voc) and short-circuit current (Isc) have exhibited a remarkable augmentation, reaching 1.05V and 31.6µA, respectively. The demonstration of effectively tailoring carrier dynamics via electrode configuration expands the practicality by achieving high power density and elucidating how the water-induced carrier density modulation occurs in 2D nanomaterials.

A sustainable and metal-free advanced oxidation process for efficient water purification by electrified reduced graphene oxide membrane

A sustainable and metal-free advanced oxidation process for efficient water purification by electrified reduced graphene oxide membrane

High antifouling graphene membranes with Fe2O3 nanoparticles in-situ intercalation for selective dye/salt separation

Effective organic dyes selective separation from high salinity textile wastewater consisting of inorganic salts and organic dyes is of great significant for the textile wastewater treatment. Graphene oxide (GO) have been used widely to form ultrathin high-permeance membrane for molecular and ionic sieving. However, swelling and membrane fouling of GO membrane hampered its practical applications. In this work, high stability and antifouling reduced graphene oxide (rGO) membranes were prepared, and Fe2O3 nanoparticles was used as intercalation to turn the membrane interlayer spacing. The rGO/2Fe2O3 nanocomposite blended membrane exhibited high permeance of 24.90 L m−2 h−1 bar−1, excellent organic dyes rejection (98.15 % and 98.69 % for methylene blue and Evans blue, respectively) and low salt retention (6.26 % for NaCl). Meanwhile, this membrane demonstrated a superior selective dye/salt separation factor up to 232 with a high rejection of 99.59 % to Evans blue and a lower salt rejection of 5.03 % to NaCl. Furthermore, nanofiltration experiments towards Evans blue/NaCl mixed solution indicated that the membrane also exhibited excellent antifouling performance with flux recovery rate of >86 % after six fouling/backwash cycles. Therefore, our work may provide a promising idea for the development of two-dimensional nanofiltration membranes for efficient high salinity textile wastewater treatment.

A new suggestion to marine gold extraction: Utilizing reduced graphene oxide membranes within seawater desalination processes

Traditional mining practices not only cause severe environmental issues, but also face the problem of insufficient production capacity of gold to meet its growing demand. The proposed alternative strategies for gold production, such as the extraction of gold from seawater, still keep a formidable challenge due to their strong dependence on adsorbent materials with high capacity, selectivity, and sensitivity, while also needing to meet the demands of being environmentally friendly and cost-effective. In practice, the direct extraction of gold from seawater is limited by its extremely low yield and high energy expenditure. However, if the combination of gold extraction techniques with seawater desalination can substantially reduce the energy consumption, the extraction of gold from seawater will become economical and feasible. In this paper, we evaluate the feasibility of marine gold extraction using reduced graphene oxide membranes (rGOM) during the seawater desalination process. The rGOM can adsorb almost all Au3+ from the solutions with trace concentrations of Au3+ ranging from 10 ppb to 200 ppb. The adsorption quantity is linearly related to the concentration, indicating that the adsorption capacity of rGOM is much higher than the total amount of Au3+ in the solution. Additionally, the rGOM can selectively adsorb 99 % of Au3+ in the mixed solution while hardly adsorbing other common elements in seawater. More importantly, the rGOM exhibits the long-term stability over 30 days when being immersed in the solution, making it directly compatible with the existing seawater desalination processes. These specific properties allow the rGOM to be an ideal candidate for combining the extraction of gold from seawater with seawater desalination processes. Our findings provide a methodology for enhancing the economic efficiency of the extraction of gold from seawater and hold promise for addressing the problem of gold scarcity.

Discrimination of Xylene Isomers by Precisely Tuning the Interlayer Spacing of Reduced Graphene Oxide Membrane.

Separating xylene isomers is a challenging task due to their similar physical and chemical properties. In this study, we developed a molecular sieve incorporating a reduced graphene oxide (rGO) membrane for the precise differentiation of xylene isomers. We fabricated GO membranes using a vacuum filtration technique followed by thermal-induced reduction to produce rGO membranes with precisely controllable interlayer spacing. Notably, we could finely tune the interlayer spacing of the rGO membrane from 8.0 to 5.0 Å by simply varying the thermal reduction temperature. We investigated the reverse osmosis separation ability of the rGO membranes for xylene isomers and found that the rGO membrane with an interlayer spacing of 6.1 Å showed a high single component permeance of 0.17 and 0.04 L m-2 h-1 bar-1 for para- and ortho-xylene, respectively, exhibiting clear permselectivity. The separation factor reached 3.4 and 2.8 when 90:10 and 50:50 feed mixtures were used, respectively, with permeance 1 order of magnitude higher than that of current state-of-the-art reverse osmosis membranes. Additionally, the membrane showed negligible permeance and selectivity decay even after continuous operation for more than 5 days, suggesting commendable membrane resistance to solvent swelling and operating pressure.

Polyoxometalate Clusters Confined in Reduced Graphene Oxide Membranes for Effective Ion Sieving and Desalination.

Efficient 2D membranes play a critical role in water purification and desalination. However, most 2D membranes, such as graphene oxide (GO) membranes, tend to swell or disintegrate in liquid, making precise ionic sieving a tough challenge. Herein, the fabrication of the polyoxometalate clusters (PW12) intercalated reduced graphene oxide (rGO) membrane (rGO-PW12) is reported through a polyoxometalate-assisted in situ photoreduction strategy. The intercalated PW12 result in the interlayer spacing in the sub-nanometer scale and induce a nanoconfinement effect to repel the ions in various salt solutions. The permeation rate of rGO-PW12 membranes are about two orders of magnitude lower than those through the GO membrane. The confinement of nanochannels also generate the excellent non-swelling stability of rGO-PW12 membranes in aqueous solutions up to 400 h. Moreover, when applied in forward osmosis, the rGO-PW12 membranes with a thickness of 90nm not only exhibit a high-water permeance of up to 0.11790 L m-2 h-1 bar-1 and high NaCl rejection (98.3%), but also reveal an ultrahigh water/salt selectivity of 4740. Such significantly improved ion-exclusion ability and high-water flux benefit from the multi-interactions and nanoconfinement effect between PW12 and rGO nanosheets, which afford a well-interlinked lamellar structure via hydrogen bonding and van der Waals interactions.

In situ oxidation of reduced graphene oxide membranes by peracetic acid for dye desalination

Graphene oxide (GO) membranes with tunable interlayer spacings are of interest for dye removal from salty textile wastewater, and the membranes are often reduced to improve their stability, which inevitably lowers water permeance. Herein, we demonstrate that reduced GO (rGO) membranes can be facilely modified using peracetic acid (PAA) in situ to dramatically enhance water permeance while retaining dye rejection. Specifically, PAA-modified membranes (PrGO) are synthesized by vacuum-filtering hydrazine-reduced rGO nanosheets onto Nylon substrate and then exposing them to PAA solutions. The effects of the rGO layer thickness, PAA content, and PAA exposure time on the membrane chemistry, nanostructures, and salt/dye separation properties are thoroughly examined. For example, the PAA oxidation of a 100 nm-thick rGO membrane for 10 min increases water permeance by 180 %, from 35 to 93 Liter m−2 h−1 bar−1, and decreases Na2SO4 rejection from 10 % to 3.3 % while retaining the rejection of Congo red at ≈99.7 %. The PrGO membranes exhibit stable water permeance and >99 % dye rejection in multi-cycle tests in a crossflow system, surpassing state-of-the-art GO membranes and showcasing their potential for practical applications.

Reduced Graphene-Oxide-Doped Elastic Biodegradable Polyurethane Fibers for Cardiomyocyte Maturation.

Conductive biomaterials offer promising solutions to enhance the maturity of cultured cardiomyocytes. While the conventional culture of cardiomyocytes on nonconductive materials leads to more immature characteristics, conductive microenvironments have the potential to support sarcomere development, gap junction formation, and beating of cardiomyocytes in vitro. In this study, we systematically investigated the behaviors of cardiomyocytes on aligned electrospun fibrous membranes composed of elastic and biodegradable polyurethane (PU) doped with varying concentrations of reduced graphene oxide (rGO). Compared to PU and PU-4%rGO membranes, the PU-10%rGO membrane exhibited the highest conductivity, approaching levels close to those of native heart tissue. The PU-rGO membranes retained anisotropic viscoelastic behavior similar to that of the porcine left ventricle and a superior tensile strength. Neonatal rat cardiomyocytes (NRCMs) and human-induced pluripotent stem cell-derived cardiomyocytes (hiPSC-CMs) on the PU-rGO membranes displayed enhanced maturation with cell alignment and enhanced sarcomere structure and gap junction formation with PU-10%rGO having the most improved sarcomere structure and CX-43 presence. hiPSC-CMs on the PU-rGO membranes exhibited a uniform and synchronous beating pattern compared with that on PU membranes. Overall, PU-10%rGO exhibited the best performance for cardiomyocyte maturation. The conductive PU-rGO membranes provide a promising matrix for in vitro cardiomyocyte culture with promoted cell maturation/functionality and the potential for cardiac disease treatment.

Electrostatic-induced ion-confined partitioning in graphene nanolaminate membrane for breaking anion–cation co-transport to enhance desalination

Constructing nanolaminate membranes made of two-dimensional graphene oxide nanosheets has gained enormous interest in recent decades. However, a key challenge facing current graphene-based membranes is their poor rejection for monovalent salts due to the swelling-induced weak nanoconfinement and the transmembrane co-transport of anions and cations. Herein, we propose a strategy of electrostatic-induced ion-confined partitioning in a reduced graphene oxide membrane for breaking the correlation of anions and cations to suppress anion-cation co-transport, substantially improving the desalination performance. The membrane demonstrates a rejection of 95.5% for NaCl with a water permeance of 48.6 L m−2 h−1 bar−1 in pressure-driven process, and it also exhibits a salt rejection of 99.7% and a water flux of 47.0 L m−2 h−1 under osmosis-driven condition, outperforming the performance of reported graphene-based membranes. The simulation and calculation results unveil that the strong electrostatic attraction of membrane forces the hydrated Na+ to undergo dehydration and be exclusively confined in the nanochannels, strengthening the intra-nanochannel anion/cation partitioning, which refrains from the dynamical anion-cation correlations and thereby prevents anions and cations from co-transporting through the membrane. This study provides guidance for designing advanced desalination membranes and inspires the future development of membrane-based separation technologies.

Distinct ion transport behavior between graphene oxide and UV-irradiated reduced graphene oxide membranes

Graphene oxide (GO) membranes are promising materials for achieving selective ion permeation in aqueous solutions. However, the swelling of GO laminates, caused by the affinity of water molecules for oxygen-containing groups (OCGs) on GO, significantly limits the practical prospects of GO membranes for selective ion transport and separation applications. Selectively removing OCGs from GO has been shown to decrease the interlayer distance between individual GO sheets, thereby improving the ability of laminate membranes to discriminate between different ions based on a size-exclusion mechanism. In this work, GO reduced through exposure to ultraviolet light (UV-rGO) is shown to display ion transport behavior that raises questions about size-exclusion as the dominant mechanism determining selective ion transport in GO membranes. Notably, smaller monovalent Li+ cations are found to permeate more slowly through UV-rGO membranes than larger divalent metal cations such as Ca2+ and Mg2+. This unexpected behavior results in a 3 – 4 fold improvement in the separation selectivity between these representative cations with UV-rGO compared to pristine GO membranes. Through a joint experimental and theoretical study, we identified the factors influencing selective ion transport through the nanochannels in UV-rGO membranes. We demonstrate that the selective removal of hydroxyl (–OH) groups from the basal planes of GO enhances the interactions of metal cations with functional groups located at the edges of GO, thereby resulting in a lower ratio of free Li+ in solution, rather than stationary Li+ adsorbed onto the surface GO, compared to Ca2+ cations. Based on these results, we propose a separation mechanism analogous to chromatography, which emphasizes the crucial role of different OCGs on GO surfaces in controlling selective ion transport through GO membranes.

Metal cation crosslinked, partially reduced graphene oxide membranes with enhanced stability for high salinity, produced water treatment by pervaporative separation

Graphene oxide (GO)-based membranes hold significant promise for applications ranging from energy storage to protective coatings, to saline water and produced water treatment, owing to their chemical stability and unique barrier properties achieving a high selectivity for water permeation. However, unmodified GO membranes are not stable when submerged in liquid water, creating challenges with their commercial utilization in aqueous filtration and pervaporation applications. To mitigate this, we develop an approach to modify GO membranes through a combination of low temperature thermal reduction and metal cation crosslinking. We demonstrate that Zn2+–rGO and Fe3+–rGO membranes had the highest permeation flux of 8.3 ± 1.5 l m−2 h−1 and 7.0 ± 0.4 l m−2 h−1, for saline water separation, respectively, when thermally reduced after metal cross-linking; These membranes maintained a high flux of 7.5 ± 0.7 l m−2 h−1, and 5.5 ± 0.3 l m−2 h−1 for produced water separation, respectively. All the membranes had a salt rejection higher than 99%. Fe3+ crosslinked membranes presented the highest organic solute rejections for produced water of 69%. Moreover, long term pervaporation testing was done for the Zn2+–rGO membrane for 12 h, and only a minor drop of 6% in permeation flux was observed, while Zn2+–GO had a drop of 24%. Both modifiers significantly enhanced the stability with Fe3+–rGO membranes displaying the highest mechanical abrasion resistance of 95% compared to non-reduced and non-crosslinked GO. Improved stability for all samples also led to higher selectivity to water over organic contaminants and only slightly reduced water flux across the membrane.

Building ordered graphene membranes by intermediate layer assisted stacking method for promoted desalination

Laminar separation membranes stacked by graphene and its derivatives hold the merit of controlled mass transfer behaviors. However, precise ion separation is challenged by the disordered assembly of nanosheets on macroporous substrates with complicated surface properties. Herein, we prepare ultrathin ordered graphene membranes by an intermediate layer assisted stacking method. Nanoporous covalent organic framework (COF) nanosheets are first vacuum-filtered on macroporous substrates, followed by deposition and thermal reduction of graphene oxide nanosheets to deliver ultrathin reduced graphene oxide (rGO) layers. The COF-decorated substrates provide a hydrophilic surface with reduced pores and roughness, facilitating the formation of ultrathin rGO layers with ordered stacking patterns and reduced microporous defects. Consequently, the obtained rGO/COF composite membranes can reject ∼90% of Na2SO4, ∼50% of NaCl, and >98% of various organic dyes, which are higher than pure rGO membranes. Meanwhile, the rGO/COF composite membranes can maintain good stability in solutions with different pH values and salt concentrations, and can be long-term operated for at least 10 days. This work is expected to deepen the understanding of the structure of laminar membranes and provides new perspectives to design ordered laminar membranes.

Utilization of graphene and rGO membranes for water and wastewater treatments

Abstract Water and wastewater treatment is crucial to meet the global demand for clean drinking water and attaining environmental sustainability. Using graphene oxide (GO) and reduced graphene oxide (rGO) membranes for wastewater and water treatment is innovative in tackling water pollution and water scarcity worldwide. Graphene-based membranes have been proven advantageous and effective in water purification due to their unique qualities such as increased surface area, mechanical and thermal durability, adsorbability, and antifouling and antibacterial capabilities. This chapter discusses the synthesis of graphene oxide and reduced graphene oxide membranes and their hybrid derivatives. It also discusses their applicability and challenges in wastewater purification. Ongoing research is necessary to optimize these membranes, as challenges persist in the large-scale cost-effective production for widespread use in water treatment plants.

Highly ion-selective graphene-oxide-based membranes for nanofluidic osmotic energy conversion

Graphene oxide (GO) membranes have shown great potential for water treatment and osmotic energy conversion. However, the inherent challenge with GO membranes lies in their instability in water. While reduction techniques can improve stability, they simultaneously compromise selective ion transport properties due to the loss of functional groups. Here, we report preassembly modified GO (GOTA) membranes by using tannic acid (TA) as modification reagent. It is found that the TA molecules not only act as reducing agent, enhancing the aqueous stability of the membrane by generating stacked graphitic sp2 domains but also serve as intercalating agent, improving the selective ion transport properties by creating localized areas with high charge density and enlarged interlayer spacing. The cation selective number of GOTA membranes is ∼0.94–0.89 for different salinity gradients, much better than the thermally reduced GO membranes. In energy conversion system, the output power density approaches ∼0.32 W m−2 for the artificial seawater and river water with energy conversion efficiency of 41.7%. Meanwhile, the GOTA membranes exhibit excellent structural stability in various solution environments. This work demonstrates the importance of nanofluidic structure in improving the performance of ion-selective membranes and provides insights into the construction of advanced osmotic energy conversion system.

Porous rGO/networked cellulose composite membranes: Towards enhanced nanofiltration performance of rGO-based membranes

Graphene-based materials have been widely used for the fabrication of superior separation membranes for water treatment and purification. In particular, reduced graphene oxide (rGO), which has better water stability than graphene oxide (GO), has been demonstrated to be a good building block. However, rGO laminates are characterized by narrow interlayer spacing leading to dense packing and consequently lower flux limiting their direct utilization for membrane development. In this study, we report the fabrication of networked cellulose (NC)/porous rGO composite membranes with enhanced separation performance. We observed a synergistic effect due to the incorporation of NC and the presence of nano-pores on the rGO sheets. Firstly, in addition to the enhanced hydrophilicity and mechanical stability, the presence of NC with networked fibers reduced the horizontal transport resistance within the interlayer channels due to the formation of voids and wrinkles. Secondly, in-plane pores created by H2O2 oxidation of GO effectively contributed to additional transport channels providing shortened transport length for water molecules. Results showed that composite membranes maintained stable long-term performance with a pure water permeance up to 25.1 ± 2.2 Lm−2h−1bar−1 and salt rejection of 70.2 %, 63.08 %, 17.13 % and 25.62 %, for Na2SO4, MgSO4, MgCl2 and NaCl respectively. Unlike many previously reported rGO membranes that rely on ultra-thin selective layers, this work demonstrates an effective strategy for fabricating superior rGO membranes for water treatment and desalination.

Enhancing the seawater desalination performance of multilayer reduced graphene oxide membranes by introducing in-plane nanopores: a molecular dynamics simulation study.

In this study, using MD simulation, the effect of creating in-plane nanopores in a reduced graphene oxide (rGO) membrane and the formation of a reduced nanoporous graphene oxide (rNPGO) membrane is proposed to increase salt rejection and water flux. To this end, the desalination performance of r1NPGO, r2NPGO and r4NPGO membranes, which have 1, 2 and 4 pore(s), respectively, with a diameter of 0.9 nm and the r1NPGO-3 nm membrane, which has 1 pore with an approximate diameter of 3.0 nm, was investigated and compared from a molecular point of view. The simulation results show that in the rNPGO membranes, by increasing the number of pores from 1 to 4, water flux increases by ∼6 times compared to the rGO membrane. Meanwhile, upon increasing the pore size from 0.9 to 3.0 nm, water flux is enhanced by ∼16 times compared to the rGO membrane. The simulation results also demonstrate that the rGO membrane has two paths for water penetration, which are called the interlayer pathway and in-slit pathway. Moreover, pores in the rNPGO membranes provide another additional path for water transfer by shortening the lateral size of the membranes. This path is referred to as the in-pore pathway. By increasing the size of the pore in the r1NPGO-3 nm membrane, the contribution of the in-pore pathway increases and plays an important role. Furthermore, the simulation results show that in all rGO and rNPGO membranes, the interlayer space acts as a barrier for ions. Therefore, complete salt rejection is observed. Interestingly, by increasing the pore size in the r1NPGO-3 nm membrane, this membrane still maintains complete salt rejection. The observed phenomenon can be a result of very high water flux in this membrane. By increasing water flux, the presence of water molecules around Na+ and Cl- ions decreases. As a result, the formation of Na+Cl- ionic clusters is strengthened in such a way that these clusters do not have the ability to pass through large pores of 3.0 nm.

Development in desalination and wastewater treatment: state of the art challenges, role of solar energy, and recommendations

Abstract Water purification is crucial to ensure the availability of safe and clean water for protecting human health and helping in a sustainable environment. This review explicitly provides an overview of the major developments related to seawater desalination and wastewater treatments as a unit. Anticipating these traditional independent facilities will operate together in the future mainly for economic benefits. The advances in seawater desalination are primarily focused on the production of membranes using different types of nanoparticles (CeO2, UiO-66, CS-NPs) and carboxylated multi-walled CNTs into a polyamide that provides high salt rejection (as high as 90%) with excellent selectivity and permeability. Further, the use of nanoporous reduced graphene oxide (rGO) membranes provided 27.7–62.6% desalination rates and up to 96.8% salt rejection, along with protection against membrane fouling. Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) showed excellent rejection of divalent ions during desalination. It is anticipated that the use of solar energy for membrane and thermal desalination may be promising since it reduces the reliance on fossil energy and significantly minimizes greenhouse gas emissions (up to 94%). Solar energy can integrate with the reverse osmosis (RO) process bearing the cost of energy-intensive compressors, making the RO economically attractive.