Cellulose/polyethyleneimine composites have increasingly attracted the attention of scientific community, devoted to the design and development of new synthetic strategies and materials for different application fields. In this review, after introducing the main characteristics of the two polymeric components, we provide in the second section a critical overview on the main protocols for the synthesis of these composites, considering both the several cellulose sources and forms, and the different cross-linkers and cross-linking procedures developed for this purpose, outlining advantages and limits for the reported approaches. The last section analyses the principal results obtained in different application fields. A wide discussion is dedicated to the principal use of cellulose/polyethyleneimine composites as sorbents for water remediation from heavy metal ions and organic contaminants. Subsequently, we introduce the literature describing the use of these composites, functionalized appropriately, where necessary, as drug delivery systems, sensors, and heterogeneous catalysts for organic reactions. Finally, after a brief description of other random applications, we furnish a personal analysis of actual limits and potentialities for these systems.

Nanocellulose-based materials are attracting an increasing interest for the positive role they could play in sustainable development; being originated from renewable resources. Moreover, cellulose has a high potential of recycling from both post-consumer waste and industrial waste. Both factors, i.e., recyclability and renewable resources; results are also extremely favourable in the perspective of circular economy. Despite all these positive aspects, an industrial production has yet to start. At the lab scale, many preparation methods of cellulose nanofibres (CNF) are available; here, the three most common are analysed: (1) enzymatic pre-treatment followed by homogenisation (ENZHO), (2) oxidative pre-treatment combined with homogenisation (TOHO) or (3) oxidative pre-treatment followed by sonication (TOSO). All three processes have been experimentally carried out starting from both virgin and recycled cellulose from industrial waste sludge. The environmental sustainability of these three routes is estimated by the Life Cycle Assessment (LCA) using experimental lab scale data. In this scenario, the comparative LCA has pointed out a superior performance of the ENZHO process, followed by TOHO and, lastly, by TOSO. The influence of energy consumption on the final results has been further investigated by a sensitivity analysis, showing that the TOHO and TOSO routes could reach similar performances by scaling-up the process from the laboratory. The different typology of CNF obtained by conducting the ENZHO process with respect to the TEMPO-mediated oxidation approach is also outlined as an additional element to be considered for the final selection of a suitable process.

Nanostructured materials have been recently proposed in the field of environmental remediation. The use of nanomaterials as building blocks for the design of nano-porous micro-dimensional systems is particularly promising since it can overcome the (eco-)toxicological risks associated with the use of nano-sized technologies. Following this approach, we report here the application of a nanostructured cellulose-based material as sorbent for effective removal of organic dyes from water. It consists of a micro- and nano-porous sponge-like system derived by thermal cross-linking among (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (TEMPO)-oxidized cellulose nanofibers (TOCNF), branched polyethylenimine 25 kDa (bPEI), and citric acid (CA). The sorbent efficiency was tested for four different organic dyes commonly used for fabric printing (Naphthol Blue Black, Orange II Sodium Salt, Brilliant Blue R, Cibacron Brilliant Yellow), by conducting both thermodynamic and kinetic studies. The material performance was compared with that of an activated carbon, commonly used for this application, in order to highlight the potentialities and limits of this biomass-based new material. The possibility of regeneration and reuse of the sorbent was also investigated.

The control of airborne contaminants is of great interest in improving air quality, which has deteriorated more and more in recent years due to strong industrial growth. In the last decades, cellulose has been largely proposed as suitable feedstock to build up eco-friendly materials for a wide range of applications. Herein, the issue regarding the use of cellulose to develop air-filtering systems is addressed. The review covers different cellulose-based solutions, ranging from aerogels and foams to membranes and films, and to composites, considering either particulate filtration (PM₁₀, PM_2.5, and PM_0.3) or gas and water permeation. The proposed solutions were evaluated on the bases of their quality factor (QF), whose high value (at least of 0.01 Pa⁻¹ referred to commercial HEPA (high-efficiency particulate air) filters) guarantees the best compromise between high filtration efficiency (>99%) and low pressure drop (<1 kPa/g). To face this aspect, we first analyzed the different morphological aspects which can improve the final filtration performance, outlining the importance on using nanofibers not only to increase surface area and to modulate porosity in final solutions, but also as reinforcement of filters made of different materials. Besides the description of technological approaches to improve the mechanical filtration, selected examples show the importance of the chemical interaction, promoted by the introduction of active functional groups on cellulose (nano)fibers backbone, to improve filtration efficiency without reducing filter porosity.

Nanocellulose constitutes a sustainable and biobased solution both as an efficient sorbent material for water treatment and as support for other inorganic nanomaterials with sorbent properties. Herein, we report the synthesis of a nanocomposite by deposition of in situ-generated silver nanoparticles (AgNPs) onto TEMPO-oxidized cellulose nanofibers (TOCNFs). Following an in-depth analytical investigation, we unveil for the first time the key role of AgNPs in enhancing the adsorption efficiency of TOCNF toward Cd²⁺ ions, chosen as model heavy metal contaminants. The obtained nanocomposite shows a value of Cd²⁺ sorption capacity at equilibrium from 150 mg L^-1 ion aqueous solutions of ∼116 mg g^-1 against the value of 78 mg g^-1 measured for TOCNF alone. A combination of field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray (EDX), and X-ray photoelectron spectroscopy (XPS) analyses suggests that Cd²⁺ ions are mainly adsorbed in the neighborhood of AgNPs. However, XPS characterization allows us to conclude that the role of AgNPs relies on increasing the exposure of carboxylic groups with respect to the original TOCNF, suggesting that these groups are still responsible for absorption. In fact, X-ray absorption spectroscopy (XAS) analysis of the Cd-K edge excludes a direct interaction between Ag⁰ and Cd²⁺, supporting the XPS results and confirming the coordination of the latter with carboxyl groups.

The contamination of freshwaters by heavy metals represents a great problem, posing a threat for human and environmental health. Cadmium is classified as carcinogen to humans and its mechanism of carcinogenicity includes genotoxic events. In this study a recently developed eco-friendly cellulose-based nanosponge (CNS) was investigated as a candidate in freshwater nano-remediation process. For this purpose, CdCl₂ (0.05 mg L⁻¹) contaminated artificial freshwater (AFW) was treated with CNS (1.25 g L⁻¹ for 2 h), and cellular responses were analyzed before and after CNS treatment in Dreissena polymorpha hemocytes. A control group (AFW) and a negative control group (CNS in AFW) were also tested. DNA primary damage was evaluated by Comet assay while chromosomal damage and cell proliferation were assessed by Cytome assay. AFW exposed to CNS did not cause any genotoxic effect in zebra mussel hemocytes. Moreover, DNA damage and cell proliferation induced by Cd(II) turned down to control level after 2 days when CNS were used. A reduction of Cd(II)-induced micronuclei and nuclear abnormalities was also observed. CNS was thus found to be a safe and effective candidate in cadmium remediation process being efficient in metal sequestering, restoring cellular damage exerted by Cd(II) exposure, without altering cellular physiological activity.