Compliant Iontronic Triboelectric Gels with Phase-Locked Structure Enabled by Competitive Hydrogen Bonding.

Rapid advancements in flexible electronics technology propel soft tactile sensing devices toward high-level biointegration, even attaining tactile perception capabilities surpassing human skin. However, the inherent mechanical mismatch resulting from deficient biomimetic mechanical properties of sensing materials poses a challenge to the application of wearable tactile sensing devices in human-machine interaction. Inspired by the innate biphasic structure of human subcutaneous tissue, this study discloses a skin-compliant wearable iontronic triboelectric gel via phase separation induced by competitive hydrogen bonding. Solvent-nonsolvent interactions are used to construct competitive hydrogen bonding systems to trigger phase separation, and the resulting soft-hard alternating phase-locked structure confers the iontronic triboelectric gel with Young's modulus (6.8-281.9 kPa) and high tensile properties (880%) compatible with human skin. The abundance of reactive hydroxyl groups gives the gel excellent tribopositive and self-adhesive properties (peel strength > 70 N m-1). The self-powered tactile sensing skin based on this gel maintains favorable interface and mechanical stability with the working object, which greatly ensures the high fidelity and reliability of soft tactile sensing signals. This strategy, enabling skin-compliant design and broad dynamic tunability of the mechanical properties of sensing materials, presents a universal platform for broad applications from soft robots to wearable electronics.

Unveiling the Dissolution Regularities of the Lignin-Carbohydrate Complex in Bamboo Cell Walls during Alkali Pretreatment.

Bamboo is a promising biomass resource. However, the complex multilayered structure and chemical composition of bamboo cell walls create a unique anti-depolymerization barrier, which increases the difficulty of separation and utilization of bamboo. In this study, the relationship between the connections of lignin-carbohydrate complexes (LCCs) within bamboo cell walls and their multilayered structural compositions was investigated. The chemical composition, structural properties, dissolution processes, and migration mechanisms of LCCs were analyzed. Alkali-stabilized LCC bonds were found to be predominantly characterized by phenyl glycoside (PhGlc) bonds along with numerous p-coumaric acid (PCA) linkage structures. As demonstrated by the NMR and CLSM results, the dissolution of the LCC during the alkaline pretreatment process was observed to migrate from the inner secondary wall (S-layer) of the bamboo fiber cell walls to the cell corner middle lamella (CCML) and compound middle lamella (CML), ultimately leading to its release from the bamboo. Furthermore, the presence of H-type lignin-FA-arabinoxylan linkage structures within the bamboo LCC was identified with their primary dissolution observed in the S-layer of the bamboo fiber cell walls. The study results provided a clear target for breaking down the anti-depolymerization barrier in bamboo, signifying a major advancement in achieving the comprehensive separation of bamboo components.

Lightweight and Strong Cellulosic Triboelectric Materials Enabled by Cell Wall Nanoengineering.

As intelligent technology surges forward, wearable electronics have emerged as versatile tools for monitoring health and sensing our surroundings. Among these advancements, porous triboelectric materials have garnered significant attention for their lightness. However, these materials face the challenge of improving structural stability to further enhance the sensing accuracy of triboelectric sensors. In this study, a lightweight and strong porous cellulosic triboelectric material is designed by cell wall nanoengineering. By tailoring of the cell wall structure, the material shows a high mechanical strength of 51.8 MPa. The self-powered sensor constructed by this material has a high sensitivity of 33.61 kPa-1, a fast response time of 36 ms, and excellent pressure detection durability. Notably, the sensor still enables a high sensing performance after the porous cellulosic triboelectric material exposure to 200 °C and achieves real-time feedback of human motion, thereby demonstrating great potential in the field of wearable electronic devices.

Anaerobic biotransformation of hexachlorocyclohexane isomers in aqueous condition: Dual CCl isotope fractionation and impact on microbial community compositions.

Hexachlorocyclohexane (HCH) isomers are persistent organic pollutants (POPs) with high toxicity, lipid solubility, chemical stability. Despite the current ban on usage of Lindane, residual contamination cannot be ignored, and HCH are frequently detected in groundwater and threaten human health. Cultures capable of degrading α-HCH, ß-HCH, γ-HCH, and δ-HCH individually have been enriched in anoxic aqueous conditions. Compound-Specific Isotope Analysis (CSIA) was applied to examine the transformation mechanisms of different HCH isomers by the four enrichment cultures. 16S rRNA sequencing techniques were employed to examine the community composition of the enrichment cultures and detect changes in these communities resulting from adding individual HCH isomers. The results indicated that the ability of the enrichment cultures for dichloroelimination of HCH isomers was inconsistent. During dichloroelimination, different bond cleavage mode of ß- and δ-HCH led to distinct isotopic effects. HCH isomers had significant impact on the microbial community, while different microbial communities showed comparable isotopic effects during the transformation of a specific HCH isomer. In addition, bacteria in the phyla Proteobacteria and Firmicutes were proposed as the dominant dechlorinators. This study provides a novel perspective on the mode of bond cleavage during HCH dichloroelimination and the effect of HCH on microbial communities, which could potentially support the evaluation of HCH transformation by CSIA and their effects on the microecosystems of groundwater.

High Strength and Toughness Polymeric Triboelectric Materials Enabled by Dense Crystal-Domain Cross-Linking.

Lightweight, easily processed, and durable polymeric materials play a crucial role in wearable sensor devices. However, achieving simultaneously high strength and toughness remains a challenge. This study addresses this by utilizing an ion-specific effect to control crystalline domains, enabling the fabrication of a polymeric triboelectric material with tunable mechanical properties. The dense crystal-domain cross-linking enhances energy dissipation, resulting in a material boasting both high tensile strength (58.0 MPa) and toughness (198.8 MJ m-3), alongside a remarkable 416.7% fracture elongation and 545.0 MPa modulus. Leveraging these properties, the material is successfully integrated into wearable self-powered devices, enabling real-time feedback on human joint movement. This work presents a valuable strategy for overcoming the strength-toughness trade-off in polymeric materials, paving the way for their enhanced applicability and broader use in diverse sensing applications.

New breakthrough in rapid degradation of lignin derivative compounds · A novel high stable and reusable green organic photocatalyst.

The pulp and paper sectors are thriving yet pose significant environmental threats to water bodies, mainly due to the substantial release of pollutants. Lignin-derived compounds are among the most problematic of these contaminants. To address this issue, we present our initial results on utilizing organic semiconductor photocatalysis under visible light for treating lignin-derived compounds. Our investigation has been centered around creating a green and cost-effective organic semiconductor photocatalyst. This catalyst is designed using a structure of bagasse cellulose spheres to support PM6 (poly[(2,6-(4,8-bis(5-(2-ethylhexyl)-4-fluorothiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene))-co-(1,3-di(5-thiophene-2-yl)-5,7-bis(2-ethylhexyl)-benzo[1,2-c:4,5-c']dithiophene-4,8-dione))]: MeIC (3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-cyclopentane-1,3-dione[c]-1-methyl-thiophe))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']-dithiophene)). This photocatalyst demonstrates remarkable efficiency, achieving over 91 % degradation of lignin-derived compounds. The superior photocatalytic performance is attributed to three main factors: (1) The ability of PM6 to broaden MeIC's absorption range from 300 to 800 nm, allowing for effective utilization of visible light; (2) the synergistic interaction between PM6 and MeIC, which ensures compatible energy levels and a vast, evenly spread surface area, promoting charge mobility and extensive donor/acceptor interfaces. This synergy significantly enhances the generation and transport of carriers, resulting in a high production of free radicals that accelerate the decomposition of organic materials; (3) The deployment of PM6:MeIC on biomass-based carriers increases the interaction surface with the organic substances. Notably, PM6: MeIC showcases outstanding durability, with its degradation efficiency remaining between 84 % and 91 % across 100 cycles. This study presents a promising approach for designing advanced photocatalysts aimed at degrading common pollutants in papermaking wastewater.

A Novel Non-Fullerene D-A Interface with Two Asymmetrical Electron Acceptors Facilitates Charge and Energy Transfer for Effective Carbon Dioxide Reduction.

Converting carbon dioxide (CO2 ) into high-value chemicals using solar energy remains a formidable challenge. In this study, the CSC@PM6:IDT6CN-M:IDT8CN-M non-fullerene small-molecule organic semiconductor is designed with highly efficient electron donor-acceptor (D-A) interface for photocatalytic reduction of CO2 . Atomic Force Microscope and Transmission Electron Microscope images confirmed the formation of an interpenetrating fibrillar network after combination of donor and acceptor. The CO yield from the CSC@PM6:IDT6CN-M:IDT8CN-M reached 1346 µmol g-1  h-1 , surpassing those of numerous reported inorganic photocatalysts. The D-A structure effectively facilitated charge separation to enable electrons transfer from the PM6 to IDT6CN-M:IDT8CN-M. Meanwhile, attributing to the dipole moments of the strong intermolecular interactions between IDT6CN-M and IDT8CN-M, the intermolecular forces are enhanced, and laminar stacking and π-π stacking are strengthened, thereby reinforcing energy transfer between acceptor molecules and significantly enhanced charge separation. Moreover, the strong internal electric field in the D-A interface enhanced the excited state lifetime of PM6:IDT6CN-M:IDT8CN-M. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis demonstrated that carboxylate (COOH*) is the predominant intermediate during CO2 reduction, and possible pathways of CO2 reduction to CO are deduced. This study presents a novel approach for designing materials with D-A interface to achieve high photocatalytic activity.

Salinity stress results in ammonium and nitrite accumulation during the elemental sulfur-driven autotrophic denitrification process.

In this study, we investigated the effects of salinity on elemental sulfur-driven autotrophic denitrification (SAD) efficiency, and microbial communities. The results revealed that when the salinity was ≤6 g/L, the nitrate removal efficiency in SAD increased with the increasing salinity reaching 95.53% at 6 g/L salinity. Above this salt concentration, the performance of SAD gradually decreased, and the nitrate removal efficiency decreased to 33.63% at 25 g/L salinity. Approximately 5 mg/L of the hazardous nitrite was detectable at 15 g/L salinity, but decreased at 25 g/L salinity, accompanied by the generation of ammonium. When the salinity was ≥15 g/L, the abundance of the salt-tolerant microorganisms, Thiobacillus and Sulfurimonas, increased, while that of other microbial species decreased. This study provides support for the practical application of elemental sulfur-driven autotrophic denitrification in saline nitrate wastewater.

Biomass-Derived Carbon Quantum Dots Chemical Bonding with Sn-Doped Bi2 O2 CO3 Endowed Fast Carriers' Dynamics and Stabilized Oxygen Vacancies for Efficient Decontamination of Combined Pollutants.

Surface defects on photocatalysts could promote carrier separation and generate unsaturated sites for chemisorption and reactant activation. Nevertheless, the inactivation of oxygen vacancies (OVs) would deteriorate catalytic activity and limit the durability of defective materials. Herein, bagasse-derived carbon quantum dots (CQDs) are loaded on the Sn-doped Bi2 O2 CO3 (BOC) via hydrothermal procedure to create Bi─O─C chemical bonding at the interface, which not only provides efficient atomic-level interfacial electron channels for accelerating carriers transfer, but also enhances durability. The optimized Sn-BOC/CQDs-2 achieves the highest photocatalytic removal efficiencies for levofloxacin (LEV) (88.7%) and Cr (VI) (99.3%). The elimination efficiency for LEV and Cr (VI) from the Sn-BOC/CQDs-2 is maintained at 55.1% and 77.0% while the Sn-BOC is completely deactivated after four cycle tests. Furthermore, the key role of CQDs in stabilization of OVs is to replace OVs as the active center of H2 O and O2 adsorption and activation, thereby preventing reactant molecules from occupying OVs. Based on theoretical calculations of the Fukui index and intermediates identification, three possible degradation pathways of LEV are inferred. This work provides new insight into improving the stability of defective photocatalysts.

Divalent manganese stimulates the removal of nitrate by anaerobic sludge.

This study investigated the effect of different concentrations of Mn2+ on the removal of nitrate by anaerobic sludge and changes in the microbial communities through batch experiments. The results showed that the addition of Mn2+ promoted nitrate removal by anaerobic sludge; the nitrate was completely removed within 6 d in the treatment group with >5 mM Mn2+. With the increase in Mn2+, the concentration of nitrite and nitrous oxide increased in the first 4 d and then decreased to 0 µM after 8 d of incubation. The increasing tendency of ammonium increased firstly and then decreased with the addition of Mn2+ compared to A. Moreover, the Mn2+ removal efficiency gradually decreased with the increase of Mn2+ concentration. The changes of microflora structure in sludge before and after adding Mn2+ were analyzed, and the results revealed that the microbial communities in the sludge may have evolved towards an energy-efficient association of short-cut nitrification, denitrification, and anaerobic ammonia oxidation after adding Mn2+. Mn2+ stimulated the removal of nitrate by anaerobic sludge mainly by promoting the growth of PHOS-HE36.

Influence of organic matters on the adsorption-desorption of 1,2-dichloroethane on soil in water and model saturated aquifer.

1,2-Dichloroethane (1,2-DCA) is a typical organic chlorinated compound largely utilized in chemical manufacturing and industrial production and also a common pollutant in organically contaminated sites. The adsorption of 1,2-DCA on soil grains significantly influences its environmental fate and removal process. This study investigated the influence of fulvic acid (FA) and humic acid (HA) on the adsorption-desorption of 1,2-DCA in solid-liquid interfaces in water or constructed porous media. Experimental findings demonstrated the influence of organic matter on the adsorption of 1,2-DCA at the solid-water interface. 1,2-DCA adsorption increased in the FA or HA-treated soils when organic matter was present on the solid surfaces. The 1,2-DCA adsorption in the mixture of FA and HA was slightly lower than that in single organic acids, depending on the binding of FA and HA to the soil grains/colloids. Basic conditions reduced the adsorption of 1,2-DCA on soils, whereas acidic conditions enhanced adsorption due to the increased interactions via adsorption sites and hydrogen bonds. Conversely, the presence of organic matter in solutions (liquid phase in constructed porous media) will reduce the adsorption of 1,2-DCA on solid surfaces and increase the transport in the model aquifer. The combination of FA, HA, and rhamnolipids is helpful for the removal of 1,2-DCA from solid surfaces. Additionally, because of the enhanced desorption, the risk of 1,2-DCA contamination in groundwater can be increased when the organic matter or surfactant is present in the liquid phase if the eluent is not collected. This study helps to better understand the cooperative interaction of soil organic matter and chlorinated hydrocarbons at solid-water interfaces and the environmental fate and potential removal strategies of chlorinated hydrocarbons in contaminated sites.

A Tough Monolithic-Integrated Triboelectric Bioplastic Enabled by Dynamic Covalent Chemistry.

Electronic waste is a growing threat to the global environment and human health, raising particular concerns. Triboelectric devices synthesized from sustainable and degradable materials are a promising electronic alternative, but the mechanical mismatch at the interface between the polymer substrate and the electrodes remains unresolved in practical applications. This study uses the sulfhydryl silanization reaction and the chemical selectivity and site specificity of the thiol-disulfide exchange reaction in dynamic covalent chemistry to prepare a tough monolithic-integrated triboelectric bioplastic. The stress is dissipated by covalent bond adaptation to the interface interaction, which makes the polymer dielectric layer to the conductive layer have a good interface adhesion effect (220.55 kPa). The interfacial interlocking of the polymer substrate with the conductive layer gives the triboelectric bioplastic excellent tensile strength (87.4 MPa) and fracture toughness (33.3 MJ m-3). Even when subjected to a tension force of 10 000 times its weight, it still maintains a stable triboelectric output with no visible cracks. This study provides new insights into the design of reliable and environmentally friendly self-powered devices, which is significant for the development of flexible wearable electronics.

Versatile Mesoporous All-Wood Sponge Enabled by In Situ Fibrillation toward Indoor-Outdoor Energy Management and Conversion.

The on-demand regulation of cell wall microstructures is crucial for developing wood as a functional building material for energy management and conversion. Here, a novel strategy based on reactive deep eutectic solvent is developed to one-step in situ fibrillate wood via disrupting the hydrogen bonding networks in cell walls and simultaneously carboxylating wood components, without significantly altering the native hierarchical structures of wood. Benefiting from its distinctive cell wall structure composed of individualized yet well-organized lignocellulose nanofibrils, in situ fibrillated wood exhibits a prominent mesoporous structure with a specific surface area of 81 m2/g. It represents a robust sponge material (5 MPa at 80% strain) with excellent durability. Due to the enhanced compressibility and charge polarization capacity, the in situ fibrillated wood (10 × 11 × 12 mm3) can generate a piezoelectric output voltage of up to 2 V under 221 kPa stress. The favorable microstructural characteristics render in situ fibrillated wood with highly thermal-insulating properties, high solar reflectivity, and mid-infrared emissivity, favoring outdoor passive cooling effects with a subambient temperature drop of 6 °C. Combining its controllable, durable, and eco-friendly attributes, our developed wood sponge represents a versatile structural material suitable for indoor/outdoor energy-saving applications.

Dissolution behavior of ionic liquids for different ratios of lignin and cellulose in the preparation of nanocellulose/lignin blends.

Lignin is regarded as a potential solution for boosting the strength of cellulose-based products. However, the mechanism of co-solubilization for lignin and cellulose has not been investigated. In this study, the effect of lignin content on the interaction between lignin and nanocellulose during lignin/cellulose co-dissolution was examined. The results revealed that lignin binds to nanocellulose throughout the dissolution process to limit the degradation of cellulose and to prepare nanocellulose/lignin composites. Moreover, the S units in lignin were more likely to interact with cellulose during the dissolution process, whereas the G units were more likely to condense. However, when the lignin content exceeded 30 wt%, the excess lignin created a severe condensation reaction, which led to a decrease in the lignin content bound to cellulose, resulting in an unequal dissolution of cellulose. Thus, a small amount of lignin attached to cellulose during the co-dissolution of lignin and cellulose inhibits cellulose degradation and can be utilized to create nanocellulose/lignin to extend the potential applications of nanocellulosic materials.

hROS-Responsive Behavior for Long-Term Stability of Cellulosic Gold Nanoclusters.

Understanding the gold core-ligand interaction in gold nanoclusters (GNCs) is essential for the on-demand tailoring of their photoluminescence properties and long-term stability. Here, inspired by the suckers arranged directionally on the tentacles of octopus, a series of GNCs with regulating ligand structures are grown and stabilized on the cellulose nanocrystals (CNCs). The carboxylated CNCs providing an electron-rich environment to promote the luminescence of GNCs and stabilize it within a long-term of 1 year through anchoring and diluting effects, and the highest quantum yields reaches 31.02% in ultrapure water. Interestingly, this bionic preparation strategy is generally applicable to various ligands for tailoring on-demand hROS-responsive and nonresponsive GNCs to construct tunable-emission wavelength dual GNCs ratiometric probes. The results show that designing a specific ligand structure to inhibit the transformation of Au-Au to Au (I)-ligand in GNCs is crucial to regulate the hROS-responsive characteristics. As expected, the interfacial compatible dual GNCs ratiometric probe with a hROS limit of detection of 0.74 µmol L-1 can diagnose certain diseases through intracellular hROS imaging. This work provides important insights for understanding the gold core-ligand interaction in GNCs during the oxidation process triggered by intracellular hROS.

Recent Advances in Flexible CNC-Based Chiral Nematic Film Materials.

Cellulose nanocrystal (CNC) is a renewable resource derived from lignocellulosic materials, known for its optical permeability, biocompatibility, and unique self-assembly properties. Recent years have seen great progresses in cellulose nanocrystal-based chiral photonic materials. However, due to its inherent brittleness, cellulose nanocrystal shows limitations in the fields of flexible materials, optical sensors and food freshness testing. In order to solve the above limitations, attempts have been made to improve the flexibility of cellulose nanocrystal materials without destroying their structural color. Despite these progresses, a systematic review on them is lacking. This review aims to fill this gap by providing an overview of the main strategies and the latest research findings on the flexibilization of cellulose nanocrystal-based chiral nematic film materials (FCNM). Specifically, typical substances and methods used for their preparation are summarized. Moreover, different kinds of cellulose nanocrystal-based composites are compared in terms of flexibility. Finally, potential applications and future challenges of flexible cellulose nanocrystal-based chiral nematic materials are discussed, inspiring further research in this field.

Dynamic Thermostable Cellulosic Triboelectric Materials from Multilevel-Non-Covalent Interactions.

Triboelectric materials present great potential for harvesting huge amounts of dispersed energy, and converting them directly into useful electricity, a process that generates power more sustainably. Triboelectric nanogenerators (TENGs) have emerged as a technology to power electronics and sensors, and it is expected to solve the problem of energy harvesting and self-powered sensing from extreme environments. In this paper, a high-temperature-resistant triboelectric material is designed based on multilevel non-covalent bonding interactions, which achieves an ultra-high surface charge density of 192 µC m-2 at high temperatures. TENGs based on the triboelectric material exhibit more than an order of magnitude higher power output (2750 mW m-2 at 200 °C) than the existing devices at high temperatures. These remarkable properties are achieved based on enthalpy-driven molecular assembly in highly unbonded states. Thus, the material maintains bond strength and ultra-high surface charge density in entropy-dominated high-temperature environments. This molecular design concept points out a promising direction for the preparation of polymers with excellent triboelectric properties.

Design of Single-Atom Catalysts for E lectrocatalytic Nitrogen Fixation.

The Electrochemical nitrogen reduction reaction (ENRR) can be used to solve environmental problems as well as energy shortage. However, ENRR still faces the problems of low NH3 yield and low selectivity. The NH3 yield and selectivity in ENRR are affected by multiple factors such as electrolytic cells, electrolytes, and catalysts, etc. Among these catalysts are at the core of ENRR research. Single-atom catalysts (SACs) with intrinsic activity have become an emerging technology for numerous energy regeneration, including ENRR. In particular, regulating the microenvironment of SACs (hydrogen evolution reaction inhibition, carrier engineering, metal-carrier interaction, etc.) can break through the limitation of intrinsic activity of SACs. Therefore, this Review first introduces the basic principles of NRR and outlines the key factors affecting ENRR. Then a comprehensive summary is given of the progress of SACs (precious metals, non-precious metals, non-metallic) and diatomic catalysts (DACs) in ENRR. The impact of SACs microenvironmental regulation on ENRR is highlighted. Finally, further research directions for SACs in ENRR are discussed.

High Toughness, Multi-dynamic Self-Healing Polyurethane for Outstanding Energy Harvesting and Sensing.

Triboelectric nanogenerators (TENGs) are an emerging class of energy harvesting devices with considerable potential across diverse applications, including wearable electronic devices and self-powered sensors. However, sustained contact, friction, and incidental scratches during operation can lead to a deterioration in the electrical output performance of the TENG, thereby reducing its overall service life. To address this issue, we developed a self-healing elastomer by incorporating disulfide bonds and metal coordination bonds into the polyurethane (PU) chain. The resulting elastomer demonstrated exceptional toughness, with a high value of 85 kJ m-3 and an impressive self-healing efficiency of 85.5%. Specifically, the TENG based on that self-healing PU elastomer generated a short circuit current of 12 µA, an open circuit voltage of 120 V, and a transfer charge of 38.5 nC within a 2 cm × 2 cm area, operating in contact-separation mode. With an external resistance of 20 MΩ, the TENG achieved a power density of 2.1 W m-2. Notably, even after self-healing, the electrical output performance of the TENG was maintained at 95% of the undamaged device. Finally, the self-healing TENG was employed to construct a self-powered noncontact sensing system that can be applied to monitor human motion accurately. This research may expand the application prospects of PU materials in future human-computer interaction and self-powered sensing fields.

Recent Advances in Tailored Fabrication and Properties of Biobased Self-Healing Polyurethane.

With the emergence of challenges in the environmental degradation and resource scarcity fields, the research of biobased self-healing polyurethane (BSPU) has become a prevailing trend in the technology of the polyurethane industry and a promising direction for developing biomass resources. Here, the production of BSPU from lignocellulose, vegetable oil, chitosan, collagen, and coumarin is classified, and the principles of designing polyurethane based on compelling examples using the latest methods and current research are summarized. Moreover, the impact of biomass materials on self-healing and mechanical properties, as well as the tailored performance method, are presented in detail. Finally, the applications of BSPU in biomedicine, sensors, coatings, etc. are also summarized, and the possible challenges and development prospects are explored to helpfully make progress in the development of BSPU. These findings demonstrate valuable references and practical significance for future BSPU research.