Development of a spiropyran-assisted cellulose aerogel with switchable wettability as oil sorbent for oil spill cleanup.

This research presents the successful development and optimization of a spiropyran-assisted cellulose aerogel (CNF-SP) aerogel with UV-induced switchable wettability, and the evaluation of its performance as an effective oil sorbent for oil spill cleanup. The aerogel initially exhibited strong hydrophobicity (124°) and showed UV-induced switchable wettability due to the photo-response structure of spiropyran. Upon UV irradiation, the hydrophobicity of the aerogel could be switched to hydrophilicity (31°), while visible light irradiation could restore its hydrophobicity. The three-dimensional (3D) porous structure of the CNF-SP aerogel combined with the hydrophobic properties of spiropyranol led to its great oil adsorption performance (27-30 g/g of oil adsorption ratio). The central composite design (CCD) was applied to optimize the aerogel and investigate the effects of raw material ratio (i.e., carboxymethyl cellulose, carboxyethyl spiropyran, polyvinyl alcohol, and nano zinc oxide) on the oil sorption performance of the aerogel. The optimized CNF-SP aerogel demonstrated a high oil sorption efficiency, particularly in acid and cold environments. Moreover, the switchable function indicated that the aerogel exhibited reusability and renewability, with the added benefit of UV-induced oil recovery.

Effects of Freeze-Drying Processes on the Acoustic Absorption Performance of Sustainable Cellulose Nanocrystal Aerogels.

Cellulose aerogels have great prospects for noise reduction applications due to their sustainable value and superior 3D interconnected porous structures. The drying principle is a crucial factor in the preparation process for developing high-performance aerogels, particularly with respect to achieving high acoustic absorption properties. In this study, multifunctional cellulose nanocrystal (CNC) aerogels were conveniently prepared using two distinct freeze-drying principles: refrigerator conventional freezing (RCF) and liquid nitrogen unidirectional freezing (LnUF). The results indicate that the rapid RCF process resulted in a denser CNC aerogel structure with disordered larger pores, causing a stronger compressive performance (Young's modulus of 40 kPa). On the contrary, the LnUF process constructed ordered structures of CNC aerogels with a lower bulk density (0.03 g/cm3) and smaller apertures, resulting in better thermal stability, higher diffuse reflection across visible light, and especially increased acoustic absorption performance at low-mid frequencies (600-3000 Hz). Moreover, the dissipation mechanism of sound energy in the fabricated CNC aerogels is predicted by a designed porous media model. This work not only paves the way for optimizing the performance of aerogels through structure control, but also provides a new perspective for developing sustainable and efficient acoustic absorptive materials for a wide range of applications.

Additive Manufacturing of Nanocellulose Aerogels with Structure-Oriented Thermal, Mechanical, and Biological Properties.

Additive manufacturing (AM) is widely recognized as a versatile tool for achieving complex geometries and customized functionalities in designed materials. However, the challenge lies in selecting an appropriate AM method that simultaneously realizes desired microstructures and macroscopic geometrical designs in a single sample. This study presents a direct ink writing method for 3D printing intricate, high-fidelity macroscopic cellulose aerogel forms. The resulting aerogels exhibit tunable anisotropic mechanical and thermal characteristics by incorporating fibers of different length scales into the hydrogel inks. The alignment of nanofibers significantly enhances mechanical strength and thermal resistance, leading to higher thermal conductivities in the longitudinal direction (65 mW m-1 K-1) compared to the transverse direction (24 mW m-1 K-1). Moreover, the rehydration of printed cellulose aerogels for biomedical applications preserves their high surface area (≈300 m2 g-1) while significantly improving mechanical properties in the transverse direction. These printed cellulose aerogels demonstrate excellent cellular viability (>90% for NIH/3T3 fibroblasts) and exhibit robust antibacterial activity through in situ-grown silver nanoparticles.

An overview of cellulose aerogels and foams for oil sorption: Preparation, modification, and potential of 3D printing.

Sorption is one of the most efficient methods to remediate the increasing oil spill incidents, but the currently available absorbents are inadequate to tackle such a global threat. Recently, numerous researchers have attempted to develop sustainable oil sorbents. Cellulose aerogels and foams, a type of lightweight porous material with excellent sorption performance, are one of the most promising candidates. Significant progress has been made in the past decade towards the development of cellulose porous materials as effective oil sorbents, with improvements in their oil sorption capacity, reusability, and enhanced multifunctionality, indicating their potential for oil spill remediation. This article reviews recent reports and provides a comprehensive overview of the preparation and modification strategies for cellulose porous materials, with a specific emphasis on their oil sorption performance and structure control. We also focus on the burgeoning 3D printing technology within this field, summarizing the latest advances with a discussion of the potential for using 3D printing to customize and optimize the structure of cellulose porous materials. Lastly, this review addresses current limitations and outlines future directions for development.

Superwetting PVA/cellulose aerogel with asymmetric structure for oil/water separation and solar-driven seawater desalination.

Extracting clean water from oily wastewater and seawater is one of the effective strategies to alleviate the freshwater crisis. However, achieving both high separation efficiency and excellent salt resistance remain challenges for materials. Herein, a novel methyltrichlorosilane-modified polyvinyl alcohol/cellulose aerogel (MPCA) was prepared by freeze drying, chemical cross-linking, and chemical vapor deposition (CVD) methods. The superwetting MPCA presented an asymmetric structure, in which the small dense pores at the top surface facilitated the efficient separation of water-in-oil (W/O) emulsions and the large pores on the bottom surface were beneficial for brine exchange. The as-prepared superwetting aerogel was suitable for the separation of various W/O emulsions with excellent separation flux (631.9-2368.7 L·m-2·h-1) and outstanding separation efficiency (99.5 %). In addition, MPCA achieved a high evaporation efficiency of 1.39 kg·m-2·h-1 and a satisfactory energy conversion efficiency of 89.7 %. Moreover, the unique asymmetric structure endowed the evaporator excellent salt resistance and could self-dissolve the accumulated salt in 20 min. The as-prepared MPCA could achieve efficient W/O emulsion separation as well as produce freshwater in seawater, providing a new strategy for oily waste seawater purification.

Wet-Stable Lamellar Wood Sponge with High Elasticity and Fatigue Resistance Enabled by Chemical Cross-Linking.

The excessive consumption of fossil-based plastics and the associated environmental concerns motivate the increasing exploitation of sustainable biomass-based materials for advanced applications. Natural wood-derived lamellar wood sponges via a top-down approach have recently attracted significant attention; however, the insufficient compressive fatigue resistance and lack of structural stability in water limit their wide applications. Here, we report a facile chemical cross-linking strategy to tackle these challenges, by which the cellulose fibrils in the lamellas are covalently bridged to enhance their connectivity. The cross-linked wood sponges demonstrate high compressibility up to 70% strain and exceptional compressive fatigue resistance (∼5% plastic deformation after 10,000 cycles at 50% strain). The interfibrillar cross-linking inhibits the swelling of cellulose fibrils and preserves the arch-shaped lamellas of the sponge in water, endowing the wood sponge with excellent wet stability. Such highly elastic and wet-stable lamellar wood sponges offer a sustainable alternative to synthetic polymer-based sponges used in diverse applications.

Development of silanized bacterial cellulose aerogels for the incorporation of natural oils with healing properties: Copaiba (Copaifera officinalis), bourbon geranium (Pelargonium X ssp.) essential oils and buriti (Mauritia flexuosa) vegetable oil.

Bacterial cellulose (BC) represents a promising biomaterial, due to its unique and versatile properties. We report, herein, on purposely-designed structural modifications of BC that enhance its application as a wound dressing material. Chemical modification of the functional groups of BC was performed initially to introduce a hydrophobic/oleophilic character to its surface. Specifically, silanization was carried out in an aqueous medium using methyltrimethoxisilane (MTMS) as the silanizing agent, and aerogels were subsequently prepared by freeze-drying. The BC-MTMS aerogel obtained displayed a highly porous (99 %) and lightweight structure with an oil absorption capacity of up to 52 times its dry weight. The XRD pattern indicated that the characteristic crystallographic planes of the native BC were maintained after the silanization process. Thermal analysis showed that the thermal stability of the BC-MTMS aerogel increased, as compared to the pure BC aerogel (pBC). Moreover, the BC-MTMS aerogel was not cytotoxic to fibroblasts and keratinocytes. In the second step of the study, the incorporation of natural oils into the aerogel's matrix was found to endow antimicrobial and/or healing properties to BC-MTMS. Bourbon geranium (Pelargonium X ssp.) essential oil (GEO) was the only oil that exhibited antimicrobial activity against the tested microorganisms, whereas buriti (Mauritia flexuosa) vegetable oil (BVO) was non-cytotoxic to the cells. This study demonstrates that the characteristics of the BC structure can be modified, while preserving its intrinsic features, offering new possibilities for the development of BC-derived materials for specific applications in the biomedical field.

Tree transpiration-inspired cellulose aerogel with engineered cold-evaporated surface for promoting structural stability and minimizing energy loss.

Solar-driven evaporation technology could significantly relieve the fresh-water crisis in the world. However, several problems, such as poor structural stability, low photothermal conversion capacity, and single heat source of traditional evaporators limited the promotion of fresh-water production efficiency. Herein, inspired by tree transpiration, we report a hydrophilic three-dimensional (3D) cellulose-based evaporator similar to the root of a tree, which can pump the bottom water to the evaporation surface for vapor generation. The aldehyde-based cellulose nanocrystals/ethylene imine polymer (ACP) aerogel was developed through Schiff base reaction to enhance the chain entangle capacity of the cellulose nanocrystals (CNCs) aerogel in water. Coating the ACP aerogel with lignin-derived photothermal material created the double-layered solar-driven evaporator (ACP-7LM), achieving a remarkable surface temperature of 35.9 °C in water under 1 sun irradiation for 1 h. The ACP-7LM exhibited an impressive evaporation rate of 1.60 kg m-2 h-1, leveraging its structural stability and excellent photothermal conversion. Increasing the cold evaporation surface (adjusting exposure height from 0 cm to 4 cm) of ACP-7LM aerogel maintained a lower temperature compared to ambient temperature on the side surface during evaporation, which harvest heat energy from environment and minimize energy loss. This enhanced environmental heat absorption boosted the ACP-7LM's evaporation rate to 3.76 kg m-2 h-1, a 2.35-fold increase over the ACP-7LM (0 cm). This solar-driven evaporator offers an efficient, innovative approach to elevate evaporation rates and address the global water crisis by simultaneously enhancing heat absorption capacity and photothermal conversion efficiency.

Adsorbent based on MOF-5/cellulose aerogel composite for adsorption of organic dyes from wastewater.

Industries persistently contribute to environmental pollution by releasing a multitude of harmful substances, including organic dyes, which represent a significant hazard to human health. As a result, the demand for effective adsorbents in wastewater treatment technology is steadily increasing so as to mitigate or eradicate these environmental risks. In response to this challenge, we have developed an advanced composite known as MOF-5/Cellulose aerogel, utilizing the Pampas plant as a natural material in the production of cellulose aerogel. Our investigation focused on analyzing the adsorption and flexibility characteristics of this novel composite for organic dye removal. Additionally, we conducted tests to assess the aerogel's reusability and determined that its absorption rate remained consistent, with the adsorption capacity of the MOF-5/cellulose aerogel composite only experiencing a marginal 5% reduction. Characterization of the material was conducted through XRD analysis, revealing the cubic structure of MOF aerogel particles under scanning electron microscopy. Our study unequivocally demonstrates the superior adsorption capabilities of the MOF-5/cellulose aerogel composite, particularly evident in its efficient removal of acid blue dye, as evaluated meticulously using UV-Vis spectrophotometric techniques. Notably, our findings revealed an impressive 96% absorption rate for the anionic dye under acidic pH conditions. Furthermore, the synthesized MOF-5/cellulose aerogel composite exhibited Langmuir isotherm behavior and followed pseudo-second-order kinetics during the absorption process. With its remarkable absorption efficiency, MOF-5/cellulose aerogel composites are poised to emerge as leading adsorbents for water purification and various other applications.

Green Strong Cornstalk Rind-Based Cellulose-PVA Aerogel for Oil Adsorption and Thermal Insulation.

Cellulose-based aerogel has attracted considerable attention for its excellent adsorption capacity, biodegradability, and renewability. However, it is considered eco-unfriendly due to defibrillation of agriculture waste and requires harmful/expensive chemical agents. In this study, cornstalk rind-based aerogel was obtained via the following steps: green H2O2/HAc delignification of cornstalk rind to obtain cellulose fibers, binding with carboxymethyl cellulose (CMC)/polyvinyl alcohol (PVA) and freeze-drying treatment, and hydrophobic modification with stearic acid. The obtained aerogel showed high compressive strength (200 KPa), which is apparently higher (about 32 kPa) than NaClO-delignified cornstalk-based cellulose/PVA aerogel. Characterization of the obtained aerogel through SEM, water contact angle, etc., showed high porosity (95%), low density (0.0198 g/cm-3), and hydrophobicity (water contact angle, 159°), resulting in excellent n-hexane adsorption capacity (35 g/g), higher (about 29.5 g/g) than NaClO-delignified cornstalk-based cellulose/PVA aerogel. The adsorbed oil was recovered by the extrusion method, and the aerogel showed excellent recyclability in oil adsorption.

Efficient solar-driven crude oil cleanup via graphene/cellulose aerogel with radial and centrosymmetric design.

Frequent oil spills pose significant threats to ecosystems; therefore, strict requirements are needed for prompt remediation and reclamation of spilled oil. Influenced by the structure of coniferous trees and their water transport, this experiment used cellulose nanofiber (CNF), polyvinyl alcohol (PVA), and methyltrimethoxysilane (MTMS) to prepare radially centrosymmetric aerogels. By utilizing the in-situ polycondensation reaction of MTMS, CNF, and PVA were connected, and the hydrophobicity and mechanical properties of the aerogel were greatly enhanced. Furthermore, the introduction of graphene oxide (GO), enshrouded within the cross-linked network, engenders heightened photo-thermal effects. The resultant composite aerogel exhibits expeditious oil absorption under solar irradiation and radial layered channel architecture, significantly curtailing the crude oil absorption timeframe (achieving a maximum absorption capacity of 51.7 g/g). Moreover, it demonstrates superior performance in rapidly and repeatedly adsorbing highly viscous crude oil, surpassing existing literature. Notably, continuous absorption of high-viscosity crude oil is achieved by integrating the composite aerogel with a peristaltic pump. This study offers a novel approach to the absorption and retrieval of high-viscosity crude oil, broadening the potential application horizons of CNF-based aerogels within environmental remediation.

Cellulose aerogel beads and monoliths from CO2-based reversible ionic liquid solution.

The CO2-based reversible ionic liquid solution of 1,1,3,3-tetramethylguanidine (TMG) and ethylene glycol (EG) in dimethyl sulfoxide (DMSO) after capturing CO2, (2[TMGH]+[O2COCH2CH2OCO2]2-/DMSO (χRILs = 0.1), provides a sustainable and effective platform for cellulose dissolution and homogeneous utilization. Highly porous cellulose aerogel beads and monoliths were successfully prepared via a sol-gel process by extruding cellulose solution into different coagulation baths (NaOH aqueous solution or alcohols) and exposing the cellulose solution in open environment, respectively, and followed by different drying techniques, including supercritical CO2-drying, freeze-drying and air-drying. The effect of the coagulation baths and drying protocols on the multi-scale structure of the as-prepared cellulose aerogel beads and monoliths were studied in detail, and the sol-gel transition mechanism was also studied by the solvatochromic parameters determination. High specific surface area of 252 and 207 m2/g for aerogel beads and monoliths were achieved, respectively. The potential of cellulose aerogels in dye adsorption was demonstrated.

Reduced Graphene Oxide/Cellulose Sodium Aerogel-Supported Eutectic Phase Change Material Gel Demonstrating Superior Energy Conversion and Storage Capacity toward High-Performance Personal Thermal Management.

By virtue of their capacity to absorb and release energy during the phase change process, phase change materials (PCMs) are ideal for personal thermal management (PTM). The combination of reduced graphene oxide/cellulose sodium aerogel (rGCA) and lauric acid/myristic acid binary eutectic phase change gel (LMG) creates a composite phase change material that possesses outstanding photothermal conversion capabilities, electro-thermal conversion capabilities, energy storage capabilities, and shape-stable performance. The results showed that rGCA had a maximum adsorption efficiency of 99.7% with a melting latent heat of 124.6 J g-1. The high absorption rate of rGCA to LMG is a result of the capillary force, pore characteristics, hydrogen bonding, and the π-π interaction. Notably, rGCA and LMG composite material (rGCG) exhibited an excellent photothermal conversion efficiency of 96.5% and electro-thermal conversion of 82.3%. Results indicate that binary eutectic phase change materials are more suitable for temperature regulation than single phase change materials, making them more suitable for PTM. It is anticipated that the innovative thermal comfort solution, which provides thermal shielding, thermal energy storage, self-supporting characteristics, and wearability, will offer new possibilities for the next generation of wearable PTMs.