Surface charge manipulation for improved humidity sensing of TEMPO-oxidized cellulose nanofibrils.

Cellulose-based humidity sensors have attracted great research interest due to their hydrophilicity, biodegradability, and low cost. However, they still suffer from relatively low humidity sensitivity. Due to the presence of negatively charged carboxylate groups, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibril (CNF) exhibits enhanced hydrophilicity and ion conductivity, which is considered a promising candidate for humidity sensing. In this work, we developed a facile strategy to improve the humidity sensitivity of CNF films by regulating their surface charge density. With the increase in surface charge density, both water uptake and charge carrier densities of the CNF films can be improved, enabling a humidity sensitivity of up to 44.5 % (%RH)-1, higher than that of most polymer-based humidity sensors reported in the literature. Meanwhile, the sensor also showed good linearity (R2 = 0.998) over the 15-75 % RH at 1 kHz. With these features, the CNF film was further demonstrated for applications in noncontact sensing, such as human respiration, moisture on fingertips, and water leakage, indicating the great potential of CNF film in humidity monitoring.

Effect of hornification on the isolation of anionic cellulose nanofibrils from Kraft pulp via maleic anhydride esterification.

Cellulose nanofibrils (CNF) isolation based on a catalyst-free maleic anhydride esterification has proven to be effective, however, the effects of pulp hornification on CNF isolation by this strategy have yet to be explored, which could present significant impacts for CNF isolation. Herein, dried northern bleached softwood Kraft pulp (D-NBSK) and never-dried northern bleached softwood Kraft pulp (ND-NBSK) were selected as the substrates. After esterification with maleic anhydride (MA), the esterified ND-NBSK pulp (E-ND) shows a significantly smaller size and more fragmented structure than the esterified D-NBSK pulp (E-D). Meanwhile, higher degree of esterification can be realized for the never dried pulp as compared to the dried pulp, which is corroborated by the significantly stronger characteristic peaks of CO (1720 cm-1) and -COO- (1575 cm-1) from the FTIR spectra and the higher surface charge content (0.86 ± 0.04 mmol/g vs. 0.55 ± 0.05 mmol/g). A comparison of the characteristics of the resulting CNF similarly demonstrated the negative impact of hornification. Overall, this work indicates that hornification tends to reduce the accessibility of chemical reagents to the pulp, leading to insufficient deconstruction. Such negative impact of hornification should be considered when performing nanocellulose isolation, especially when using pulp as feedstock.

Responses of multi-faceted benthic macroinvertebrates alpha and beta diversity to flooding in a highland floodplain.

Flooding is an important process in natural fluvial floodplains. How the flood shapes aquatic community diversity in highland floodplains is still poorly understood. The aim of this study was to unravel the multi-faceted responses of benthic macroinvertebrate diversity to flooding and habitat environments in the Baihe River Basin from a taxonomic, phylogenetic, and functional perspective. We examined the alpha and beta diversity patterns of benthic macroinvertebrate communities in the mainstream, tributaries, and oxbow lakes during the normal water and flood periods. The results showed that the traditional alpha taxonomic diversity (TD) varied across habitats, despite minor changes after flood pulse. Alpha phylogenetic diversity (PD) decreased and alpha functional diversity (FD) markedly increased after flooding, with functional traits transiting toward risk avoidance. While all the three facets of beta diversity significantly responded to habitat differences, beta TD and PD shifted in response to flooding. Species turnover prominently increased in beta TD and PD after flood pulse, which contrasted with a weaker response of this process in FD. The explanatory power of significant environmental factors on both alpha and beta diversity was reduced by flooding. Compared with traditional TD, cooperating multi-faceted diversity could better depict the responses of benthic macroinvertebrate communities to flooding. The assessment and conservation of aquatic biodiversity in highland floodplains should take into account the three facets of alpha and beta diversity.

Trophic level plays an enhanced role in shaping microbiota structure and assembly in lakes with decreased salinity on the Qinghai-Tibet and Inner Mongolia Plateaus.

Plateau lakes characterized by salinization and eutrophication are essential aquatic ecosystems. A myriad of microorganisms serve as crucial biological resources in plateau lakes and drive the elemental cycles of these ecosystems. Currently, there is a paucity of knowledge regarding the impacts of salinization and eutrophication dynamics on the microbiota in plateau lakes. Here, high-throughput sequencing of the 16S ribosomal RNA genes (V4 region) was used to characterize microbial community structure and assembly in plateau lakes with different salinities and trophic levels. Water samples were collected at 191 sites across 24 lakes on the Qinghai-Tibet and Inner Mongolia Plateaus in northern China. The results showed that high salinity considerably reduced microbial alpha-diversity and niche breadth while increasing within-group similarity among various lake types. High salinity additionally decreased the complexity of microbial networks and enhanced network robustness. The assembly of microbial communities was primarily governed by deterministic processes in high-salinity and eutrophic low-salinity lakes. At decreased salinity, trophic level played a leading role in shaping microbial community structure, and the ecological processes shifted from deterministic processes driven by high salinity to eutrophication-driven deterministic processes. The biomarkers also varied from taxa adapted to high-salinity environments (e.g., Nanoarchaeaeota, Rhodothermia) to those suited for living in freshwater and low-salinity habitats (e.g., Alphaproteobacteria, Actinobacteria). In the case of eutrophication, Actinobacteria, Chloroflexi, and Cyanobacteria became the dominant taxa. Our findings indicate that decreased salinity enables trophic level to play an enhanced role in shaping microbial community structure and assembly in plateau lakes. This study enriches our knowledge about the ecological impacts of salinization and eutrophication in plateau lakes.

3D Printed Cellulose Nanofiber Aerogel Scaffold with Hierarchical Porous Structures for Fast Solar-Driven Atmospheric Water Harvesting.

Hygroscopic salt-based composite sorbents are considered ideal candidates for solar-driven atmospheric water harvesting. The primary challenge for the sorbents lies in exposing more hygroscopically active sites to the surrounding air while preventing salt leakage. Herein, a hierarchically structured scaffold is constructed by integrating cellulose nanofiber and lithium chloride (LiCl) as building blocks through 3D printing combined with freeze-drying. The milli/micrometer multiscale pores can effectively confine LiCl and simultaneously provide a more exposed active area for water sorption and release, accelerating both water sorption and evaporation kinetics of the 3D printed structure. Compared to a conventional freeze-dried aerogel, the 3D printed scaffold exhibits a water sorption rate that is increased 1.6-fold, along with a more than 2.4-fold greater water release rate. An array of bilayer scaffolds is demonstrated, which can produce 0.63 g g-1 day-1 of water outdoors under natural sunlight. This article provides a sustainable strategy for collecting freshwater from the atmosphere.

Superelastic Cellulose Sub-Micron Fibers/Carbon Black Aerogel for Highly Sensitive Pressure Sensing.

Superelastic aerogels with rapid response and recovery times, as well as exceptional shape recovery performance even from large deformation, are in high demand for wearable sensor applications. In this study, a novel conductive and superelastic cellulose-based aerogel is successfully developed. The aerogel incorporates networks of cellulose sub-micron fibers and carbon black (SMF/CB) nanoparticles, achieved through a combination of dual ice templating assembly and electrostatic assembly methods. The incorporation of assembled cellulose sub-micron fibers imparts remarkable superelasticity to the aerogel, enabling it to retain 94.6% of its original height even after undergoing 10 000 compression/recovery cycles. Furthermore, the electrostatically assembled CB nanoparticles contribute to exceptional electrical conductivity in the cellulose-based aerogel. This combination of electrical conductivity and superelasticity results in an impressive response time of 7.7 ms and a recovery time of 12.8 ms for the SMF/CB aerogel, surpassing many of the aerogel sensors reported in previous studies. As a proof of concept, the SMF/CB aerogel is utilized to construct a pressure sensor and a sensing array, which exhibit exceptional responsiveness to both minor and substantial human motions, indicating its significant potential for applications in human health monitoring and human-machine interaction.

Multiscale Design for Robust, Thermal Insulating, and Flame Self-Extinguishing Cellulose Foam.

Cellulose foams are in high demand in an era of prioritizing environmental consciousness. Yet, transferring the exceptional mechanical properties of cellulose fibers into a cellulose network remains a significant challenge. To address this challenge, an innovative multiscale design is developed for producing cellulose foam with exceptional network integrity. Specifically, this design relies on a combination of physical cross-linking of the microfibrillated cellulose (MFC) networks by cellulose nanofibril (CNF) and aluminum ion (Al3+), as well as self-densification of the cellulose induced by ice-crystal templating, physical cross-linking, solvent exchange, and evaporation. The resultant cellulose foam demonstrates a low density of 40.7 mg cm-3, a high porosity of 97.3%, and a robust network with high compressive modulus of 1211.5 ± 60.6 kPa and energy absorption of 77.8 ± 1.9 kJ m-3. The introduction of CNF network and Al3+ cross-linking into foam also confers excellent wet stability and flame self-extinguish ability. Furthermore, the foam can be easily biodegraded in natural environments , re-entering the ecosystem's carbon cycle. This strategy yields a cellulose foam with a robust network and outstanding environmental durability, opening new possibilities for the advancement of high-performance foam materials.

Responses of biodiversity to microhabitat heterogeneity in debris flow gullies: Assessing the impact of hydrological disturbance.

Rivers play a vital role in the maintenance of the biosphere and human society, since they participate in the global water cycle and provide varied habitats to support biodiversity. Microhabitat heterogeneity is regarded as a key factor driving biodiversity and it plays an active ecological role in different types of mountain rivers. Whether river microhabitat heterogeneity exhibits the same ecological patterns across hydrological periods remains unclear. Here, we analyzed the changes in macroinvertebrate community composition, functional traits, and multi-faceted α-diversity in five debris flow gullies in the Xiaojiang River Basin (southwestern China) between two different hydrological periods. We explored the responses of biodiversity to river microhabitat heterogeneity and its driving factors before and after hydrological disturbance. The results indicated that river microhabitat heterogeneity and three facets of macroinvertebrate α-diversity decreased after hydrological disturbance, with macroinvertebrate state traits becoming more unbalanced. Macroinvertebrate taxonomic diversity increased with increasing river microhabitat heterogeneity across hydrological periods, and this pattern was more prominent before hydrological disturbance. A high correlation emerged between macroinvertebrate phylogenetic diversity and river microhabitat heterogeneity only before hydrological disturbance. Hydrogeomorphic parameters prominently affected macroinvertebrate communities before hydrological disturbance. Water environmental parameters worked together with hydrogeomorphic parameters to shape macroinvertebrate communities in hydrologically disturbed debris flow gullies, indicating a reduced ecological role of river microhabitat heterogeneity. The ecological health of debris flow gullies can be improved by increasing vegetation coverage on river bank slopes to increase slope stability and mitigate hydrological disturbances, as well as placing large rocks into river channels to enhance riverbed stability and create habitats for more biological groups.

Porous and conductive cellulose nanofiber/carbon nanotube foam as a humidity sensor with high sensitivity.

In this study, we developed a humidity sensor with high sensitivity based on cellulose nanofiber/carbon nanotube (CNF/CNT) hybrid foam. The porous structure of the foam not only provides more contact interface for water molecules adsorption, but also tunes the conductivity of the CCF closed to the point where the sensor is most sensitive to the change in humidity. With this porous structural design, the obtained foam sensor shows a high humidity sensitivity of 87.3% (ΔI/I0, and the response limit is 100%), excellent linearity (R2 = 0.996) within the humidity range from 29 to 95% relative humidity (RH), and good long-time stability (more than two months). Furthermore, the water vapor adsorption behavior of the CNF/CNT foam sensor can be well described by the pseudo-first-order kinetic model. Finally, a simple humidity measuring device based on the CNF/CNT foam is presented, which can find good applications for human breath and fingertip humidity monitoring.

Electrochemical Performance of Thick-Film Li(Ni0.6Mn0.2Co0.2)O2 Cathode with Hierarchic Structures and Laser Ablation.

The electrochemical performance of lithium-ion batteries is directly influenced by type of active material as well as its morphology. In order to evaluate the impact of particle morphology in thick-film electrodes, Li(Ni0.6Mn0.2Co0.2)O2 (NMC 622) cathodes with bilayer structure consisting of two different particle sizes were manufactured and electrochemically characterized in coin cells design. The hierarchical thick-film electrodes were generated by multiple casting using NMC 622 (TA) with small particle size of 6.7 µm and NMC 622 (BA) with large particle size of 12.8 µm. Besides, reference electrodes with one type of active material as well as with two type of materials established during mixing process (BT) were manufactured. The total film thickness of all hierarchical composite electrodes were kept constant at 150 µm, while the thicknesses of TA and BA were set at 1:2, 1:1, and 2:1. Meanwhile, three kinds of thin-film cathodes with 70 µm were applied to represent the state-of-the-art approach. Subsequently, ultrafast laser ablation was applied to generate groove structures inside the electrodes. The results demonstrate that cells with thin-film or thick-film cathode only containing TA, cells with bilayer electrode containing TBA 1:2, and cells with laser-structured electrodes show higher capacity at C/2 to 5C, respectively.

Characterization and Laser Structuring of Aqueous Processed Li(Ni0.6Mn0.2Co0.2)O2 Thick-Film Cathodes for Lithium-Ion Batteries.

Lithium-ion batteries have led the revolution in portable electronic devices and electrical vehicles due to their high gravimetric energy density. In particular, layered cathode material Li(Ni0.6Mn0.2Co0.2)O2 (NMC 622) can deliver high specific capacities of about 180 mAh/g. However, traditional cathode manufacturing involves high processing costs and environmental issues due to the use of organic binder polyvinylidenfluoride (PVDF) and highly toxic solvent N-methyl-pyrrolidone (NMP). In order to overcome these drawbacks, aqueous processing of thick-film NMC 622 cathodes was studied using carboxymethyl cellulose and fluorine acrylic hybrid latex as binders. Acetic acid was added during the mixing process to obtain slurries with pH values varying from 7.4 to 12.1. The electrode films could be produced with high homogeneity using slurries with pH values smaller than 10. Cyclic voltammetry measurements showed that the addition of acetic acid did not affect the redox reaction of active material during charging and discharging. Rate capability tests revealed that the specific capacities with higher slurry pH values were increased at C-rates above C/5. Cells with laser structured thick-film electrodes showed an increase in capacity by 40 mAh/g in comparison to cells with unstructured electrodes.

Electrostatic self-assembly enabled flexible paper-based humidity sensor with high sensitivity and superior durability.

Humidity sensors have been widely used for humidity monitoring in industrial fields. However, the application of conventional sensors is limited due to the structural rigidity, high cost, and time-consuming integration process. Owing to the good hydrophilicity, biodegradability, and low cost of cellulose, the sensors built on cellulose bulk materials are considered a feasible method to overcome these drawbacks while providing reasonable performance. Herein, we design a flexible paper-based humidity sensor based on conductive 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose fibers/carbon nanotubes (TOCFs/CNTs) conformal fibers network. The CNTs are dispersed by cationic cetyl trimethyl ammonium bromide (CTAB), which introduces positive charges on the CNTs surface. The conductive fibers are achieved by an electrostatic self-assembly process that positively charged CNTs are adsorbed to the surface of negatively charged TOCFs. The vast number of hydrophilic hydroxyl groups on the surface of TOCFs provide more water molecules adsorption sites and facilitate the electron transfer from water molecules to CNTs, endowing the sensor with an excellent humidity responsive property. Besides, the swelling of the TOCFs greatly damages the conductive CNTs network and further promotes the humidity sensitive performance of the sensor. Benefiting from the unique structure, the obtained sensor exhibits a maximum response value of 87.0% (ΔI/I0 , and the response limit is 100%), outstanding linearity (R2 = 0.995) between 11 and 95% relative humidity (RH), superior bending (with a curvature of 2.1 cm-1) and folding (up to 50 times) durability, and good long-time stability (more than 3 months). Finally, as a proof of concept, the sensor demonstrates an excellent responsive property to human breath, fingertip humidity, and the change of air humidity, indicating a great potential towards practical applications.

Cellulose Nanofiber/Carbon Nanotube Dual Network-Enabled Humidity Sensor with High Sensitivity and Durability.

Humidity sensors have been widely used for humidity monitoring in industrial fields, while the unsatisfactory flexibility, time consumption, and expensive integration process of conventional inorganic sensors significantly limit their application in wearable electronics. Using paper-based humidity sensors is considered a feasible method to overcome these drawbacks because of their good flexibility and roll-to-roll manufacturability, while they still face problems such as poor durability and low sensitivity. In this study, we report a high-performance paper-based humidity sensor based on a rationally designed bilayered structure consisting of a nanoporous cellulose nanofiber/carbon nanotube (CNF/CNT) sensitive layer and a microporous paper substrate. The vast number of hydrophilic hydroxyl groups on the surface of CNF and paper fibers enables fast water molecule exchange between the humidity-sensitive material and the external environment via hydrogen bonding, endowing the paper-based sensor with an excellent humidity responsive property. The obtained sensor displays a maximum response value of 65.0% (ΔI/I0) at 95% relative humidity. Furthermore, the mechanical interlocking structure formed between the CNF/CNT layer and the paper layer provides the sensor with strong interlayer adhesion. Benefiting from the unique structure, the sensor also exhibits outstanding bending (with a maximum curvature of 22.2 cm-1) and folding durability (up to 50 times). Finally, as a proof of concept, a simple humidity-measuring device is assembled, which demonstrates an excellent responsive property toward human breath and the change of air humidity, indicating a great potential of our paper-based humidity sensor toward practical applications.

Responses of macroinvertebrate functional traits to riverbed structure of typical debris flow gullies in the upper reaches of the Yangtze River, China.

Debris flow is a typical natural disaster in mountainous areas. Its occurrence has serious impacts on the ecological environment and the life, property safety of local people. The structure of mountain riverbed plays an important role in maintaining the ecological stability of debris flow gullies (DFGs) and improving the ecological condition. However, the effects of hydro-geomorphological processes induced by riverbed structure on local macroinvertebrates have not been well examined. A functional approach was applied to macroinvertebrate data collected in a field survey at sites with different riverbed structure to investigate the response of macroinvertebrate functional traits and environment factors to riverbed structure-induced processes. Riverbed structure was quantitatively calculated by concavity-convexity degree. The results showed that (a) Macroinvertebrates were mainly composed of individuals with the ability of avoiding risks and recovering quickly in DFGs. (b) The environmental factors affecting macroinvertebrates (i.e., average particle size, velocity, flow rate, water depth, and gradient) had a great relationship with riverbed structure. (c) Only 3 (trophic habit, attachment and drift) of the 10 benthic functional traits in the study area had a good correlation with riverbed structure. This study thus found that riverbed structure, as a complex of various environmental factors directly or indirectly affected the community structure and functional traits of macroinvertebrates in DFGs. Besides, it was more suitable for macroinvertebrates of different species to live, and more conducive to the maintenance of ecological stability when the concavity-convexity degree value was about 0.075. Because 5 environmental factors affecting macroinvertebrates were moderate when the degree of concavity was about 0.075. These results can provide scientific basis for ecological conservation and management in DFGs where eco-environment is very fragile.

Phytoplankton in the heavy sediment-laden Weihe River and its tributaries from the northern foot of the Qinling Mountains: community structure and environmental drivers.

The Weihe River Basin plays an indispensable role in the water environment and water ecological balance in Northwest China and the lower reaches of the Yellow River. In the context of river ecosystems being affected by climate change and human activities, phytoplankton, as primary producers in food webs, serve as an important ecological indicator of environmental change. As such, systematic surveys on the water environment and phytoplankton were carried out in the Weihe River mainstem and its five tributaries from the northern foot of the Qinling Mountains from October to November 2017 and April to May 2018. In total, 154 species of phytoplankton belonging to 69 genera were identified in the heavy sediment-laden mainstem, with an average density and biomass of 177.57*104 cell L-1 and 6.53 mg L-1, respectively. Furthermore, a total of 207 species of phytoplankton belonging to 81 genera were identified in the five tributaries originating in the Qinling Mountains, with an average density and biomass of 80.98*104 cell L-1 and 1.90 mg L-1, respectively. Canonical correspondence analysis (CCA) was employed to analyze the relationship between phytoplankton communities and environmental factors. The results of data screening and Monte Carlo sequencing tests revealed that water temperature (WT), dissolved oxygen (DO), and nitrite nitrogen (NO2--N) were the primary environmental factors affecting the distribution and abundance of phytoplankton in the Weihe River mainstem. WT, flow velocity (V), pH, conductivity (Cond), and NO2--N predominantly structured the phytoplankton communities in the Weihe River tributaries. The results of this study are useful for the ecological management and conservation of the mainstem and tributaries of the Weihe River Basin.

Flexible and Highly Sensitive Humidity Sensor Based on Cellulose Nanofibers and Carbon Nanotube Composite Film.

Flexible and highly sensitive humidity sensors are crucial for humidity detection. In this study, a flexible cellulose nanofiber/carbon nanotube (NFC/CNT) humidity sensor with high sensitivity performance was developed via fast vacuum filtration. CNTs were well dispersed in water by using 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO)-oxidized NFC as a dispersant. More importantly, NFC also acted as a humidity sensitive material, achieving superior performance of NFC/CNT humidity sensors. The obtained NFC/CNT humidity sensor with 5 wt % CNT loading exhibits outstanding sensitive performance, and its response value reaches a maximum of 69.9% (Δ I/ I0) at 95% relative humidity (RH). It also displays good bending resistance and long-term stability. In addition, the NFC/CNT humidity sensor was employed to monitor human breath. Therefore, we believe that the flexible, highly sensitive, and simply designed NFC/CNT humidity sensor is a promising candidate for various applications in the field of humidity measurement.

Highly Transparent and Self-Extinguishing Nanofibrillated Cellulose-Monolayer Clay Nanoplatelet Hybrid Films.

A viable solution toward "green" optoelectronics is rooted in our ability to fabricate optoelectronics on transparent nanofibrillated cellulose (NFC) film substrates. However, the flammability of transparent NFC film poses a severe fire hazard in optoelectronic devices. Despite many efforts toward enhancing the fire-retardant features of transparent NFC film, making NFC film fire-retardant while maintaining its high transparency (≥90%) remains an ambitious objective. Herein, we combine NFC with NFC-dispersed monolayer clay nanoplatelets as a fire retardant to prepare highly transparent NFC-monolayer clay nanoplatelet hybrid films with a superb self-extinguishing behavior. Homogeneous and stable monolayer clay nanoplatelet dispersion was initially obtained by using NFC as a green dispersing agent with the assistance of ultrasonication and then used to blend with NFC to prepare highly transparent and self-extinguishing hybrid films by a water evaporation-induced self-assembly process. As the content of monolayer clay nanoplatelets increased from 5 wt % to 50 wt %, the obtained hybrid films presented enhanced self-extinguishing behavior (limiting oxygen index sharply increased from 21% to 96.5%) while retaining a ∼90% transparency at 600 nm. More significantly, the underlying mechanisms for the high transparency and excellent self-extinguishing behavior of these hybrid films with a clay nanoplatelet content of over 30 wt % were unveiled by a series of characterizations such as SEM, XRD, TGA, and limiting oxygen index tester. This work offers an alternative environmentally friendly, self-extinguishing, and highly transparent substrate to next-generation optoelectronics, and is aimed at providing a viable solution to environmental concerns that are caused by ever-increasing electronic waste.

Programmable Shape Recovery Process of Water-Responsive Shape-Memory Poly(vinyl alcohol) by Wettability Contrast Strategy.

Water-responsive shape-memory polymers (SMPs) are desirable for biomedical applications, but their limited shape recovery process is problematic. Herein, we demonstrate a shape-memory poly(vinyl alcohol) (SM-PVA) with programmable multistep shape recovery processes in water via a wettability contrast strategy. A hexamethyldisilazane (HMDS)-treated SiO2 nanoparticle layer with varying loading weights was rationally deposited onto the surface of SM-PVA, aiming to create surface-wettability contrast. The varying wettability led to different water adsorption behaviors of SM-PVA that could be well-described by the pseudo-first-order kinetic model. The results calculated from the kinetic model showed that both the pseudo-first order-adsorption rate constant and the saturated water absorption of SM-PVA demonstrated a declining trend as the loading weight of SiO2 increased, which laid the foundation for the local regulation of the water-responsive rate of SM-PVA. Finally, two proof-of-concept drug-delivery devices with diverse three-dimensional structures and actuations are presented based on the water-responsive SM-PVA with preprogrammed multistep shape recovery processes. We believe the programmable shape-memory behavior of water-responsive SM-PVA could highly extend its use in drug delivery, tissue engineering scaffolds, and smart implantable devices, etc.