Nanocellulose-based Membranes Research Articles

Removal of heavy metal ions from water using nanocellulose-based membranes derived from macroalgae Chara corallina

Chara corallina is a freshwater macroalgae found in aquatic-terrestrial boundary environments. Their cellulose fibers have a crystallinity and biosynthesis similar to those of terrestrial plants. The algal nanocellulose (NC) was prepared through a series of chemical treatments, including alkaline, bleaching, grinding, and acid hydrolysis. The X-ray diffraction (XRD) crystallinity index of nanocellulose was 85.64%. The cellulose nanocrystals are seen in the form of nanorods, and the specific surface area of the sample of NC found was 5.823 m2g-1. The study aimed to test the effectiveness of a nanocellulose composite membrane in removing heavy metal ions, specifically cadmium (Cd), nickel (Ni), and lead (Pb) ions, from an aqueous solution. A vacuum filtration unit was used for the experiment, where up to five filter layers of composite membranes were examined for their ability to remove heavy metal ions. The results showed that the highest removal rates of Cd2+, Ni2+, and Pb2+ ions were 98.20%, 95.15%, and 93.80%, respectively, when using five layers of membranes of NC with the adsorbent dose set at 20 ppm. Cellulose and its derivatives are essential in sustainable technology for wastewater treatment, as they demonstrate exceptional performance in removing various types of pollutants, including heavy metals, dyes, and other pollutants. Cellulose is preferred due to its low cost, biodegradability, eco-friendliness, and simple surface modification.

Nanocellulose-based membranes with pH- and temperature-responsive pore size for selective separation

Smart gating membranes have drawn much attention due to the controllable pore structure. Herein, a smart gating membrane with dual responsiveness was prepared from bacteria cellulose (BC) grafted with pH- and temperature-responsive polymers. By external stimulation, the average pore size of the membrane can be controlled from 33.75 nm to 144.81 nm, and the pure water flux can be regulated from 342 to 2118 L·m−2·h−1 with remarkable variation in the pH range of 1–11 and temperature range of 20–60 °C. The adjustability of pore size is able to achieve the gradient selective separation of particles and polymers with different sizes. In addition, owing to the underwater superoleophobicity and the nanoscale pore structure, the membrane separation efficiencies of emulsified oils are higher than 99 %. Moreover, the controllable pore size endows the membrane with good self-cleaning performance. This nanocellulose-based smart gating membrane has potential applications in the fields of controllable permeation, selective separation, fluid transport, and drug/chemical controlled release systems.

Study on the Rectification of Ionic Diode Based on Cross-Linked Nanocellulose Bipolar Membranes.

Nanocellulose-based membranes have attracted intense attention in bioelectronic devices due to their low cost, flexibility, biocompatibility, degradability, and sustainability. Herein, we demonstrate a flexible ionic diode using a cross-linked bipolar membrane fabricated from positively and negatively charged cellulose nanofibrils (CNFs). The rectified current originates from the asymmetric charge distribution, which can selectively determine the direction of ion transport inside the bipolar membrane. The mechanism of rectification was demonstrated by electrochemical impedance spectroscopy with voltage biases. The rectifying behavior of this kind of ionic diode was studied by using linear sweep voltammetry to obtain current-voltage characteristics and the time dependence of the current. In addition, the performance of cross-linked CNF diodes was investigated while changing parameters such as the thickness of the bipolar membranes, the scanning voltage range, and the scanning rate. A good long-term stability due to the high density cross-linking of the diode was shown in both current-voltage characteristics and the time dependence of current.

Fabrication of cellulose nanocrystals/carboxymethyl cellulose/zeolite membranes for methylene blue dye removal: understanding factors, adsorption kinetics, and thermodynamic isotherms.

This study introduces environmentally-friendly nanocellulose-based membranes for AZO dye (methylene blue, MB) removal from wastewater. These membranes, made of cellulose nanocrystals (CNCs), carboxymethyl cellulose (CMC), zeolite, and citric acid, aim to offer eco-friendly water treatment solutions. CNCs, obtained from sugarcane bagasse, act as the foundational material for the membranes. The study aims to investigate both the composition of the membranes (CMC/CNC/zeolite/citric acid) and the critical adsorption factors (initial MB concentration, contact time, temperature, and pH) that impact the removal of the dye. After systematic experimentation, the optimal membrane composition is identified as 60% CNC, 15% CMC, 20% zeolites, and 5% citric acid. This composition achieved a 79.9% dye removal efficiency and a 38.3mg/g adsorption capacity at pH 7. The optimized membrane exhibited enhanced MB dye removal under specific conditions, including a 50mg adsorbent mass, 50ppm dye concentration, 50mL solution volume, 120-min contact time, and a temperature of 25°C. Increasing pH from neutral to alkaline enhances MB dye removal efficiency from 79.9% to 94.5%, with the adsorption capacity rising from 38.3mg/g to 76.5mg/g. The study extended to study the MB adsorption mechanisms, revealing the chemisorption of MB dye with pseudo-second-order kinetics. Chemical thermodynamic experiments determine the Freundlich isotherm as the apt model for MB dye adsorption on the membrane surface. In conclusion, this study successfully develops nanocellulose-based membranes for efficient AZO dye removal, contributing to sustainable water treatment technologies and environmental preservation efforts.

Facile construction of robust superhydrophobic ZIF‐8@pulp/cellulose nanofiber (CNF) membrane for multifunctional applications

Given the increasing contamination of freshwater supplies, it is essential to effectively treat industrial wastewater. However, treating industrial wastewater using a single method is challenging due to the presence of complex contaminants like petroleum, organic dyes, bacteria, and other complex contaminants. In this study, we present a straightforward and scalable approach to prepare multifunctional nanocellulose-based membranes (NM) that exhibit superhydrophobicity, self-cleaning, oil/water separation, photocatalysis, and anti-bioadhesion properties. To begin with, we created NM by extruding fiber slurry onto a stencil and drying it. Next, we built a polyurethane (PU)/ZIF‐8/1H, 1H, 2H, 2H‐perfluorooctyltriethoxysilane (POTS)-based superhydrophobic layer by spraying it over the NM's surface. By employing the aforementioned processes, we successfully integrated multiple functions into a single superhydrophobic NM. Our results demonstrate that the NM-PU/ZIF-8/POTS membrane exhibits superior hydrophobicity performance, with a high-water contact angle (166.8 ± 0.8°) and a low rolling angle (5 ± 0.3°). Moreover, these samples retain high-water contact angles and low rolling angles even in harsh environments such as acid and alkali solutions, high temperatures, abrasion resistance, UV aging resistance, bending and folding, tape peeling, and self-cleaning. The NM-PU/ZIF-8/POTS membrane also exhibits high and stable oil-water separation performance, with a separation efficiency of 94.6% and a relatively high separation flux (133.2 L·m−2·h−1). At the same time, the NM-PU/ZIF-8/POTS membrane exhibits water-in-oil emulsion separation ability. The membrane’s stability, effectiveness, and reusability were demonstrated through ten repetitions of degradation experiments using aqueous methylene blue solution, with the NM-PU/ZIF-8/POTS membrane exhibiting an excellent degradation rate (>94%). Finally, the bioadhesion resistance test indicated a reduction of 69.1% in the adhesion rate of the NM-PU/ZIF-8/POTS membrane. Overall, the creation of the NM-PU/ZIF-8/POTS membrane serves as a useful inspiration for the practical application of superhydrophobic NM in multifunctional integration, while also broadening the scope of membrane applications.

A comprehensive review on nanocellulose-based membranes: methods, mechanism, and applications in wastewater treatment

A comprehensive review on nanocellulose-based membranes: methods, mechanism, and applications in wastewater treatment

Current and Potential Applications of Green Membranes with Nanocellulose.

Large-scale applications of nanotechnology have been extensively studied within the last decade. By exploiting certain advantageous properties of nanomaterials, multifunctional products can be manufactured that can contribute to the improvement of everyday life. In recent years, one such material has been nanocellulose. Nanocellulose (NC) is a naturally occurring nanomaterial and a high-performance additive extracted from plant fibers. This sustainable material is characterized by a unique combination of exceptional properties, including high tensile strength, biocompatibility, and electrical conductivity. In recent studies, these unique properties of nanocellulose have been analyzed and applied to processes related to membrane technology. This article provides a review of recent synthesis methods and characterization of nanocellulose-based membranes, followed by a study of their applications on a larger scale. The article reviews successful case studies of the incorporation of nanocellulose in different types of membrane materials, as well as their utilization in water purification, desalination, gas separations/gas barriers, and antimicrobial applications, in an effort to provide an enhanced comprehension of their capabilities in commercial products.

Nanocellulose-based membrane as a potential material for high performance biodegradable aerosol respirators for SARS-CoV-2 prevention: a review.

The controversy surrounding the transmission of COVID-19 in 2020 has revealed the need to better understand the airborne transmission route of respiratory viruses to establish appropriate strategies to limit their transmission. The effectiveness in protecting against COVID-19 has led to a high demand for face masks. This includes the single-use of non-degradable masks and Filtering Facepiece Respirators by a large proportion of the public, leading to environmental concerns related to waste management. Thus, nanocellulose-based membranes are a promising environmental solution for aerosol filtration due to their biodegradability, renewability, biocompatibility, high specific surface area, non-toxicity, ease of functionalization and worldwide availability. Although the technology for producing high-performance aerosol filter membranes from cellulose-based materials is still in its initial stage, several promising results show the prospects of the use of this kind of materials. This review focuses on the overview of nanocellulose-based filter media, including its processing, desirable characteristics and recent developments regarding filtration, functionalization, biodegradability, and mechanical behavior. The porosity control, surface wettability and surface functional groups resulting from the silylation treatment to improve the filtration capacity of the nanocellulose-based membrane is discussed. Future research trends in this area are planned to develop the air filter media by reinforcing the filter membrane structure of CNF with CNCs. In addition, the integration of sol–gel technology into the production of an air filter can tailor the pore size of the membrane for a viable physical screening solution in future studies.Graphical abstract

Progress and Prospects of Nanocellulose-Based Membranes for Desalination and Water Treatment.

Membrane-based desalination has proved to be the best solution for solving the water shortage issues globally. Membranes are extremely beneficial in the effective recovery of clean water from contaminated water sources, however, the durability as well as the separation efficiency of the membranes are restricted by the type of membrane materials/additives used in the preparation processes. Nanocellulose is one of the most promising green materials for nanocomposite preparation due to its biodegradability, renewability, abundance, easy modification, and exceptional mechanical properties. This nanocellulose has been used in membrane development for desalination application in the recent past. The study discusses the application of membranes based on different nanocellulose forms such as cellulose nanocrystals, cellulose nanofibrils, and bacterial nanocellulose for water desalination applications such as nanofiltration, reverse osmosis, pervaporation, forward osmosis, and membrane distillation. From the analysis of studies, it was confirmed that the nanocellulose-based membranes are effective in the desalination application. The chemical modification of nanocellulose can definitely improve the surface affinity as well as the reactivity of membranes for the efficient separation of specific contaminants/ions.

Recent Development and Environmental Applications of Nanocellulose-Based Membranes.

Extensive research and development in the production of nanocellulose production, a green, bio-based, and renewable biomaterial has paved the way for the development of advanced functional materials for a multitude of applications. From a membrane technology perspective, the exceptional mechanical strength, high crystallinity, tunable surface chemistry, and anti-fouling behavior of nanocellulose, manifested from its structural and nanodimensional properties are particularly attractive. Thus, an opportunity has emerged to exploit these features to develop nanocellulose-based membranes for environmental applications. This review provides insights into the prospect of nanocellulose as a matrix or as an additive to enhance membrane performance in water filtration, environmental remediation, and the development of pollutant sensors and energy devices, focusing on the most recent progress from 2017 to 2022. A brief overview of the strategies to tailor the nanocellulose surface chemistry for the effective removal of specific pollutants and nanocellulose-based membrane fabrication approaches are also presented. The major challenges and future directions associated with the environmental applications of nanocellulose-based membranes are put into perspective, with primary emphasis on advanced multifunctional membranes.

The effect of crosslinking on ion transport in nanocellulose-based membranes

Ion selective membranes are at the heart of energy conversion and harvesting, water treatment, and biotechnologies. The currently available membranes are mostly based on expensive and non-biodegradable polymers. Here, we report a cation-selective and low-cost membrane prepared from renewable nanocellulose and 1,2,3,4-butanetetracarboxylic acid which simultaneously serves as crosslinker and source of anionic surface groups. Charge density and structure of the membranes are studied. By using different degrees of crosslinking, simultaneous control over both the nanochannel structure and surface charge concentration is achieved, which in turn determines the resulting ion transport properties. Increasing negative charge concentration via higher crosslinker content, the obtained ion conductivity reaches up to 8 mS/cm (0.1 M KCl). Optimal ion selectivity, also influenced by the solution pH, is achieved at 20 wt% crosslinker addition (with ion conductivity of 1.6 mS/cm). As regular ~1.4 nm nanochannels were formed at this composition, nanofluidic contribution to ion transport is likely.

Antibacterial nanocellulose membranes coated with silver nanoparticles for oil/water emulsions separation

The superhydrophilic/underwater superoleophobic nanocellulose-based membranes show great potential in oil/water emulsion separation. However, nanocellulose composed of polysaccharides inevitably suffered from bacterial erosion during use or storage, resulting in structural damage or reduced separation efficiency. In this work, silver nanoparticles (AgNPs) as effective bactericidal materials are uniformly deposited on tunicate cellulose nanocrystals (TCNCs) by in situ hydrothermal reduction of silver nitrate. TCNCs not only act as reducing agents for silver ions, but also work as dispersant and stabilizers of AgNPs. Nanocomposite membranes are fabricated by vacuum-assisted filtrating of AgNPs@TCNC suspension, which exhibit nanoporous structure, superhydrophilicity, and underwater superoleophobicity. These membranes could efficiently separate oil/water microemulsion with water flux (>324 L m−2 h−1 bar−1) and oil rejection (>99%). Importantly, these membranes show excellent antibacterial efficacy against E. coli and S. aureus, benefiting to their long-term use and storage.

A Brief Review of Nanocellulose Based Hybrid Membranes for CO2 Separation

Due to the high specific surface area, high mechanical strength and broad possibility of surface modification, nanocellulose has obtained much attention as a new class of bio-based nanomaterials with promising potential in a wide variety of applications. Recently, a considerable amount of research has been aimed to the fabrication of nanocellulose based hybrid membranes for water treatment. However, nanocellulose based hybrid gas separation membrane is still a new research area. Herein, we force on recent advancements in the fabrication methods and separation performances of nanocellulose-based hybrid membranes for CO2 separation, the transport mechanisms involved, along with the challenges in the utilization of nanocellulose in membranes. Finally, some perspectives on future R&D of nanocellulose-based membranes for CO2 separation are proposed.

Nanocellulose-Based Materials for Water Purification.

Nanocellulose is a renewable material that combines a high surface area with high strength, chemical inertness, and versatile surface chemistry. In this review, we will briefly describe how nanocellulose is produced, and present—in particular, how nanocellulose and its surface modified versions affects the adsorption behavior of important water pollutants, e.g., heavy metal species, dyes, microbes, and organic molecules. The processing of nanocellulose-based membranes and filters for water purification will be described in detail, and the uptake capacity, selectivity, and removal efficiency will also be discussed. The processing and performance of nanocellulose-based membranes, which combine a high removal efficiency with anti-fouling properties, will be highlighted.

Nanocellulose-based membranes for CO2 capture

A new type of hydrophilic polymeric membrane based on microfibrillated cellulose (MFC) has been investigated to determine its potential in the field of gas separation, with special reference to carbon capture and natural gas sweetening. In particular, pure MFC films and MFC/Lupamin® (a commercial polyvinylamine produced by BASF) nanocomposite membrane have been synthesized and characterized. The effect of relative humidity on gas permeability was considered and independent water vapor sorption experiments were also carried out in order to correlate the permeation results to the actual water content in the materials. The experimental results showed that very good CO2/N2 and CO2/CH4 selectivity (in the order of 500 and 350 respectively) could be reached by using pure MFC films, which however showed limited CO2 permeability, never exceeding 25Barrer, even at the highest relative humidity investigated. To increase the transmembrane flux, a hydrophilic polyvinylamine (Lupamin®) has been added to the pure MFC: the addition caused a marked increase in permeability of up to one order of magnitude but decreased the selectivity to about the same extent, thus decreasing the overall membrane performance. The reason of such behavior seems to be related to the amount of water absorbed by the membrane as the MFC/Lupamin nanocomposite resulted to be highly swollen by water vapor.Nonetheless, both the investigated materials showed separation performances that are above the 2008 Robeson's upper bound for CO2/N2 and CO2/CH4 systems, disclosing an attractive potential for the production of advanced gas separation membranes.