N-Vacancy Enriched Porous BN Fibers for Enhanced Polysulfides Adsorption and Conversion in High-Performance Lithium-Sulfur Batteries.

Severe shuttle effect of soluble polysulfides and sluggish redox kinetics have been thought of as the critical issues hindering the extensive applications of lithium-sulfur batteries (LSBs). Herein, one-dimensional boron nitride (1D BN) fibers with abundant pores and sufficient N-vacancy defects were synthesized using a thermal crystallization following a pre-condensation step. The 1D structure of BN facilitates unblocked ions diffusion pathways during charge/discharge cycles. The embedded pores within the polar BN strengthen the immobilization of polysulfides via both physical confinement and chemical interaction. Moreover, the highly exposed active surface area and intentionally created N-vacancy sites substantially promote reaction kinetics by lowering the energy barriers of the rate-limiting steps. After incorporating with conductive carbon networks and elemental S, the as-prepared S/Nv-BN@CBC cathode of LSBs deliver an initial discharge capacity of up to 1347 mAh g-1 at 200 mA g-1, while maintaining a low decay rate of 0.03% per cycle over 1000 cycles at 1600 mA g-1. This work offers an effective strategy to mitigate the shuttle effect and highlights the significant potential of defect-engineered BN in accelerating the reaction kinetics of LSBs.

Construction of cellulose-based hybrid hydrogel beads containing carbon dots and their high performance in the adsorption and detection of mercury ions in water.

Cellulose-based adsorbents have been extensively developed in heavy metal capture and wastewater treatment. However, most of the reported powder adsorbents suffer from the difficulties in recycling due to their small sizes and limitations in detecting the targets for the lack of sensitive sensor moieties in the structure. Accordingly, carbon dots (CDs) were proposed to be encapsulated in cellulosic hydrogel beads to realize the simultaneous detection and adsorption of Hg (II) in water due to their excellent fluorescence sensing performance. Besides, the molding of cellulose was beneficial to its recycling and further reduced the potential environmental risk generated by secondary pollution caused by adsorbent decomposition. In addition, the detection limit of the hydrogel beads towards Hg (II) reached as low as 8.8 × 10-8 M, which was below the mercury effluent standard declared by WHO, exhibiting excellent practicability in Hg (II) detection and water treatment. The maximum adsorption capacity of CB-50 % for Hg (II) was 290.70 mg/g. Moreover, the adsorbent materials also had preeminent stability that the hydrogel beads could maintain sensitive and selective sensing performance towards Hg (II) after 2 months of storage. Additionally, only 3.3% of the CDs leaked out after 2 weeks of immersion in water, ensuring the accuracy of Hg (II) evaluation. Notably, the adsorbent retained over 80% of its original adsorption capacity after five consecutive regeneration cycles, underscoring its robustness and potential for sustainable environmental applications.

MXenes Antibacterial Properties and Applications: A Review and Perspective.

The mutations of bacteria due to the excessive use of antibiotics, and generation of antibiotic-resistant bacteria have made the development of new antibacterial compounds a necessity. MXenes have emerged as biocompatible transition metal carbide structures with extensive biomedical applications. This is related to the MXenes' unique combination of properties, including multifarious elemental compositions, 2D-layered structure, large surface area, abundant surface terminations, and excellent photothermal and photoelectronic properties. The focus of this review is the antibacterial application of MXenes, which has attracted the attention of researchers since 2016. A quick overview of the synthesis strategies of MXenes is provided and then summarizes the effect of various factors (including structural properties, optical properties, surface charges, flake size, and dispersibility) on the biocidal activity of MXenes. The main mechanisms for deactivating bacteria by MXenes are discussed in detail including rupturing of the bacterial membrane by sharp edges of MXenes nanoflakes, generating the reactive oxygen species (ROS), and photothermal deactivating of bacteria. Hybridization of MXenes with other organic and inorganic materials can result in materials with improved biocidal activities for different applications such as wound dressings and water purification. Finally, the challenges and perspectives of MXene nanomaterials as biocidal agents are presented.

In Situ Reconstruction of Active Catalysis Sites Triggered by Chromium Immobilization for Sulfite Oxidation.

Hexavalent chromium (Cr(VI)) is a highly toxic substance in wastewater, triggering grievous detriment to aquatic life and human health. Magnesium sulfite is spawned along with the desulfurization process in coal-fired power plants, which is usually disposed of as solid waste. Here, a "waste control by waste" method was proposed upon the redox of Cr(VI)-sulfite, in which highly toxic Cr(VI) is detoxicated and sequent enriched on a novel biochar-induced cobalt-based silica composite (BISC) due to the forced electron transfer from chromium to surface hydroxyl. The immobilized Cr on BISC gave rise to the reconstruction of catalytic active sites "Cr-O-Co", which further enhance its performance in sulfite oxidation by elevating O2 adsorption. As a result, the sulfite oxidation rate increased by 10 times compared with the non-catalysis benchmark together with the maximum chromium adsorption capacity being 120.3 mg/g. Therefore, this study provides a promising strategy to simultaneously control highly toxic Cr(VI) and sulfite, achieving high-grade sulfur resource recovery for wet magnesia desulfurization.

Degradable polyprodrugs: design and therapeutic efficiency.

Prodrugs are developed to increase the therapeutic properties of drugs and reduce their side effects. Polyprodrugs emerged as highly efficient prodrugs produced by the polymerization of one or several drug monomers. Polyprodrugs can be gradually degraded to release therapeutic agents. The complete degradation of polyprodrugs is an important factor to guarantee the successful disposal of the drug delivery system from the body. The degradation of polyprodrugs and release rate of the drugs can be controlled by the type of covalent bonds linking the monomer drug units in the polymer structure. Therefore, various types of polyprodrugs have been developed based on polyesters, polyanhydrides, polycarbonates, polyurethanes, polyamides, polyketals, polymetallodrugs, polyphosphazenes, and polyimines. Furthermore, the presence of stimuli-responsive groups, such as redox-responsive linkages (disulfide, boronate ester, metal-complex, and oxalate), pH-responsive linkages (ester, imine, hydrazone, acetal, orthoester, P-O and P-N), light-responsive (metal-complex, o-nitrophenyl groups) and enzyme-responsive linkages (ester, peptides) allow for a selective degradation of the polymer backbone in targeted tumors. We envision that new strategies providing a more efficient synergistic therapy will be developed by combining polyprodrugs with gene delivery segments and targeting moieties.

Dansyl-labelled cellulose as dual-functional adsorbents for elimination and detection of mercury in aqueous solution via aggregation-induced emission.

Dansyl chloride fluorophore exhibits typical aggregation induced fluorescence emission behavior in acetone/water solution. To realize the integration of detective and adsorptive functions, dansyl chloride is covalently immobilized on cellulose substrate to fabricate an efficient adsorbent for mercury ions in water. The as-prepared material exhibits excellent fluorescence sensing performance exclusively for Hg (II) with the presence of other metal ions. A sensitive and selective fluorescence quenching across the concentration range of 0.1-8.0 mg/L is observed with a detection limit of 8.33 × 10-9 M as a result of the inhibition of aggregation induced emission caused by the coordination between adsorbent and Hg (II). Besides, the adsorption properties for Hg (II) including the influence of initial concentration and contact time are investigated. Langmuir model and pseudo-second-order kinetics are demonstrated to fit well with the adsorption experiment for the uptake of Hg (II) by the functionalized adsorbent, also, intraparticle diffusion kinetic model is proved to aptly describe the Hg (II) removal in aqueous solution. In addition, the recognition mechanism is considered to originate from the Hg (II) triggered structural reversals of naphthalene ring units which are verified by the X-ray photoelectron spectroscopy and density functional theory calculation. Moreover, the synthesis method used in this work also provides a strategy for the sensing application of organic sensor molecules with AIE properties in which the aggregated behavior could be appropriately realized.

Exhausted Cr(VI) Sensing/Removal Aerogels Are Recycled for Water Purification and Solar-Thermal Energy Generation.

Heavy metal pollution has resulted in numerous environmental challenges. However, classic approaches, involving the use of solid adsorbents are subject to limitations, including the high energy consumption required for processing before and after use. Accordingly, strategies that facilitate the use of metal capture media that extends beyond waste remediation are attractive. Herein, a porous fluorescent aerogel (CPC aerogel) is constructed by immersing amino-based carbon dots (CDs-NH2 ) into a polyethyleneimine (PEI)/carboxymethylated cellulose (CMC) aerogel network for the simultaneous detection and adsorption of Cr(VI). Adsorption experiments confirm that the CMC/PEI containing CDs-NH2 aerogel (CPC aerogel) exhibits good Cr(VI) extraction capacity, and can reach a level that conforms with industrial water safety standards. In addition, the CPC aerogel can continuously detect and remove Cr(VI) at high flux. Following Cr(VI) absorption, the CPC aerogel may be vulcanized (MSx -CPC gel) and used for solar thermoelectric generation resulting in power generation. Additionally, the MSx -CPC gel can be used for solar steam generation and exhibits excellent evaporation rates of ≈1.31 kg m-2 h-1 under one sun irradiation. The results serve to underscore how materials designed for metal ion recognition and adsorption once exhausted can be exploited to provide materials for solar thermoelectric power generation and seawater desalination.

Starch-Based Composite Films with Enhanced Hydrophobicity, Thermal Stability, and UV-Shielding Efficacy Induced by Lignin Nanoparticles.

Thehighly efficient utilization of lignin is of great importance for the development of the biorefinery industry. Herein, a novel "core-shell" lignin nanoparticle (LNP) with a diameter of around 135 nm was prepared, after the lignin was isolated from the effluent of formic acid fractionation via dialysis. In an attempt to endow composite materials with vital functionalities, the LNP was added to the starch film and the starch/polyvinyl alcohol (PVA) or starch/polyethylene oxide (PEO) composite film. The results showed that the hydrophobicity performance of the synthesized films was enhanced significantly. Specifically, the dynamic water contact angle value of the starch/PVA composite film with 1% (wt) addition of LNPs could be maintained as high as 122° for 180 s; the starch/PEO composite film also achieved an excellent water contact angle above 120°. The addition of LNPs promoted the formation of some rough structures on the film surface, as shown by the scanning electron microscopy images, which could repel the water molecules efficiently and are closely related to the enhanced hydrophobicity of the starch film. What is more, the as-prepared LNP conferred strengthened thermal stability and ultraviolet blocking properties on the starch composite film. The structural combination of the polymer film with LNPs holds the promise for providing advanced functionalities to the composite material with wide applications.

Porous Structure of ß-Cyclodextrin for CO2 Capture: Structural Remodeling by Thermal Activation.

With a purpose of extending the application of ß-cyclodextrin (ß-CD) for gas adsorption, this paper aims to reveal the pore formation mechanism of a promising adsorbent for CO2 capture which was derived from the structural remodeling of ß-CD by thermal activation. The pore structure and performance of the adsorbent were characterized by means of SEM, BET and CO2 adsorption. Then, the thermochemical characteristics during pore formation were systematically investigated by means of TG-DSC, in situ TG-FTIR/FTIR, in situ TG-MS/MS, EDS, XPS and DFT. The results show that the derived adsorbent exhibits an excellent porous structure for CO2 capture accompanied by an adsorption capacity of 4.2 mmol/g at 0 °C and 100 kPa. The porous structure is obtained by the structural remodeling such as dehydration polymerization with the prior locations such as hydroxyl bonded to C6 and ring-opening polymerization with the main locations (C4, C1, C5), accompanied by the release of those small molecules such as H2O, CO2 and C3H4. A large amount of new fine pores is formed at the third and fourth stage of the four-stage activation process. Particularly, more micropores are created at the fourth stage. This revealed that pore formation mechanism is beneficial to structural design of further thermal-treated graft/functionalization polymer derived from ß-CD, potentially applicable for gas adsorption such as CO2 capture.

Functionalized Masks: Powerful Materials against COVID-19 and Future Pandemics.

The outbreak of COVID-19 revealed the vulnerability of commercially available face masks. Without having antibacterial/antiviral activities, the current masks act only as filtering materials of the aerosols containing microorganisms. Meanwhile, in surgical masks, the viral and bacterial filtration highly depends on the electrostatic charges of masks. These electrostatic charges disappear after 8 h, which leads to a significant decline in filtration efficiency. Therefore, to enhance the masks' protection performance, fabrication of innovative masks with more advanced functions is in urgent demand. This review summarizes the various functionalizing agents which can endow four important functions in the masks including i) boosting the antimicrobial and self-disinfectant characteristics via incorporating metal nanoparticles or photosensitizers, ii) increasing the self-cleaning by inserting superhydrophobic materials such as graphenes and alkyl silanes, iii) creating photo/electrothermal properties by forming graphene and metal thin films within the masks, and iv) incorporating triboelectric nanogenerators among the friction layers of masks to stabilize the electrostatic charges and facilitating the recharging of masks. The strategies for creating these properties toward the functionalized masks are discussed in detail. The effectiveness and limitation of each method in generating the desired properties are well-explained along with addressing the prospects for the future development of masks.

Thiomers of Chitosan and Cellulose: Effective Biosorbents for Detection, Removal and Recovery of Metal Ions from Aqueous Medium.

Removal of toxic metal ions using adsorbents is a well-known strategy for water treatment. While chitosan and cellulose can adsorb weakly some types of metals, incorporating thiols as metal chelating agents can improve their sorption behaviors significantly. Presented in this review are the various chemical modification strategies applicable for thiolation of chitosan and cellulose in the forms of mercaptans, xanthates and dithiocarbamates. Moreover, much attention has been paid to the specific strategies for controlling the thiolation degree and characterization approaches for establishing the structure-property relationship. Also, the kinetics and isotherm models that elucidate the adsorption processes and mechanisms induced by the thiomers have been explained. These thiomers have found great potentials in the applications associated with metal removal, metal recovery and metal detection.

Biological Activities and Emerging Roles of Lignin and Lignin-Based Products─A Review.

Bioactive substances, displaying excellent biocompatibility, chemical stability, and processability, could be extensively applied in biomedicine and tissue engineering. In recent years, plant-based bioactive substances such as flavonoids, vitamins, terpenes, and lignin have received considerable attention due to their human health benefits and pharmaceutical/medical applications. Among them is lignin, an amorphous biomacromolecule mainly derived from the combinatorial radical coupling of three phenylpropane units (p-hydroxypenyl, guaiacyl, and syringyl) during lignification. Lignin possesses intrinsic bioactivities (antioxidative, antibacterial, anti-UV activities, etc.) against phytopathogens. Lignin also enhances the plant resistance (adaptability) against environmental stresses. The abundant structural features of lignin offer other significant bioactivities including antitumor and antivirus bioactivities, regulation of plant growth, and enzymatic hydrolysis of cellulose. This Review reports the latest research results on the bioactive potential of lignin and lignin-based substances in biomedicine, agriculture, and biomass conversion. Moreover, the interfacial reactions and bonding mechanisms of lignin with biotissue/cells and other constituents were also discussed, aiming at promoting the conversion or evolution of lignin from industrial wastes to value-added bioactive materials.

Antimicrobial/Biocompatible Hydrogels Dual-Reinforced by Cellulose as Ultrastretchable and Rapid Self-Healing Wound Dressing.

Hydrogels as a wound dressing, integrated with ultrastretchability, rapid self-healing, and excellent antimicrobial activity, are in high demand, particularly for joint skin wound healing. Herein, a multifunctional and ductile composite hydrogel was developed using poly(vinyl alcohol) (PVA)-borax gel as a matrix that was synergized or dual-reinforced with dopamine-grafted oxidized carboxymethyl cellulose (OCMC-DA) and cellulose nanofibers (CNF). Moreover, neomycin (NEO), an aminoglycoside antibiotic with multifunctional groups, was incorporated into the hydrogel network as both an antibacterial agent and a cross-linker. The dynamic reversible borate ester linkages and hydrogen bonds between OCMC-DA, PVA, and CNF, along with dynamic cross-linking imine linkages between NEO and OCMC-DA, endowed the hydrogel with excellent self-healing ability and stretchability (3300%). The as-reinforced networks enhanced the mechanical properties of hydrogels significantly. More remarkably, the composite hydrogel with improved biodegradability and biocompatibility is pH-responsive and effective against a broad spectrum of bacteria, which is attributed to the controllable release of NEO for steady availability of the antibiotic on the wound location. Overall, the antimicrobial hydrogel with rapid self-healing and reliable mechanical properties holds significant promise as dressing material for wound healing.

Layer-by-Layer Assembly for Surface Tethering of Thin-Hydrogel Films: Design Strategies and Applications.

Manipulation and engineering of the surfaces has a key role in improving the materials properties. Anchoring of thin hydrogels on the materials surface is one of the recently developed methods to achieve surfaces with high potential applications. Layer-by-layer (LBL) has been used widely as a strong strategy for immobilization of thin hydrogel films on the surface of various organic/inorganic substrates. Electrostatic LBL and covalent LBL are two main strategies used in this regard. In electrostatic LBL, negatively and positively hydrophilic polymers are sequentially assembled to create a multilayer hydrogel which subsequent covalent crosslinking of multilayers improved the stability of the inserted layers. On the other hand, covalent LBL requires hydrophilic polymers bearing reactive telechelic groups. These reactive polymers are prepared by various polymerization techniques or by post-functionalization of biopolymers. The principles of hydrogel anchoring have described along with representative examples. Besides, the potential applications of the modified surfaces in specific cases have been addressed and overviewed.

Natural Polymer-Based Antimicrobial Hydrogels without Synthetic Antibiotics as Wound Dressings.

Wound healing is usually accompanied by bacterial infection. The excessive use of synthetic antibiotics leads to drug resistance, posing a significant threat to human health. Hydrogel-based wound dressings aimed at mitigating bacterial infections have emerged as an effective wound treatment. The review presented herein particularly focuses on the hydrogels originating from natural polymers. To further enhance the performance of wound dressings, various strategies and approaches have been developed to endow the hydrogels with excellent broad-spectrum antibacterial activity. Those that are summarized in the current review are the hydrogels with intrinsic or stimuli-triggered bactericidal properties and others that serve as vehicles for loading antibacterial agents without synthetic antibiotics. Specific attention is paid to antimicrobial mechanisms and the antibacterial performance of hydrogels. Practical antibacterial applications to accelerate the wound healing employing these antibiotic-free hydrogels are also introduced along with the discussion on the current challenges and perspectives leading to new technologies.

Suppressing Ammonia Re-Emission with the Aid of the Co3O4-NPs@KIT-6 Catalyst in Ammonia-Based Desulfurization.

The re-emission of NH3 and SO2 caused by the decomposition of (NH4)2SO3 is a crucial concern in ammonia-based desulfurization. In this study, a novel Co3O4-NPs@KIT-6 catalyst with a three-dimensional two-helix structure is proposed for converting (NH4)2SO3 into (NH4)2SO4. The oxidation rate of (NH4)2SO3 with the catalyst was 7.5 times that without any catalyst, and this improvement was attributed to appropriately dispersed Co3O4 nanoparticles with a size of 4-10 nm that interacted with the KIT-6 support. Therefore, the number of active sites with substitution and hole defects was substantially increased, which is advantageous for high catalytic activities. Consequently, the amount of NH3 and SO2 re-emission during (NH4)2SO3 oxidation was reduced by 43.9%, which considerably reduced potential environmental risks. The results of this study serve to advance ammonia desulfurization by improving the desulfurization efficiency, downsizing the oxidation tank, and generating considerable profit from efficient reclaiming of (NH4)2SO4 as a fertilizer.

Study on cellulose microfilaments based composite spheres: Microwave-assisted synthesis, characterization, and application in pollutant removal.

A novel study of synthesizing the temperature-responsive polymer grafted cellulose filaments/Poly (N-isopropylacrylamide) (NIPAM) spheres (P-MCCBs) was carried out for the removal of dyes and heavy metal ions. The novelty of the presented work consists of the application of the nano-sized pore-forming agent (Calcium Carbonate) and the introduction of a temperature-responsive monomer (NIPAM) while preparing the adsorbents. In addition, the spherical adsorbents were synthesized through an in-situ free radical polymerization using a microwave-assisted heating approach. The morphology, chemical structure, pH, and thermal sensitivity of P-MCCBs were characterized properly. The adsorption and desorption behaviors of dyes and heavy metal ions on P-MCCBs were also investigated. The results showed that P-MCCBs exhibited a fast adsorption rate, the adsorption equilibrium reached within 80 min and 40 min for MB and Pb2+, respectively (25 °C). Moreover, around 5-8% and 20% of adsorbed MB and Pb2+ were released at the temperature above 45 °C. The adsorption kinetics followed pseudo-second-order model, and the desorption process was fit well using Higuchi and Korsmeyer-Peppas models. These results indicated that P-MCCBs could be served as a novel material for controllable adsorption and desorption processes of various contaminants.

Inhibiting Mercury Re-emission and Enhancing Magnesia Recovery by Cobalt-Loaded Carbon Nanotubes in a Novel Magnesia Desulfurization Process.

Mercury re-emission, because of the reduction of Hg2+ to form Hg0 by sulfite, has become a great concern in the desulfurization process. Lowering the concentrations of Hg2+ and sulfite in the desulfurization slurry can retard the Hg0 formation and, thus, mitigate mercury re-emission. To that end, cobalt-based carbon nanotubes (Co-CNTs) were developed for the simultaneous Hg2+ removal and sulfite oxidation in this work. Furthermore, the thermodynamics and kinetics of the Hg2+ adsorption and effect of Hg2+ adsorption on catalytic activity of Co-CNTs were investigated. Experimental results revealed that the Co-CNTs not only accelerated sulfite oxidation to enable the recovery of desulfurization by-products but also acted as an effective adsorbent of Hg2+ removal. The Hg2+ adsorption rate mainly depended on the structure of the adsorption material regardless of the cobalt loading and morphological distribution. The catalytic activity of the Co-CNTs for sulfite oxidation was not significantly affected due to the Hg2+ adsorption. Additionally, the isothermal adsorption behavior was well-fitted to the Langmuir model with an adsorption capacity of 166.7 mg/g. The mercury mass balance analysis revealed that the Hg0 re-emission was decreased by 156% by adding 2.0 g/L of Co-CNTs. These results can be used as a reference for the simultaneous removal of multiple pollutants in the wet-desulfurization process.

Characterization of Conformation and Locations of C-F Bonds in Graphene Derivative by Polarized ATR-FTIR.

It is still a challenge to explore the orientation and location of chemical groups in the two-dimensional derivative of graphene. In this study, polarized attenuated total reflectance Fourier transform infrared spectroscopy (polarized ATR-FTIR) was employed to investigate the orientation and location of C-F groups in the corresponding graphene derivative sheets, which facilitates building a relationship between the bonding nature and fine structure. There were two types of C-F bonding, (C-F)I and (C-F)II, in fluorinated graphene sheets. It was found that (C-F)II bonds were linked at the coplanar carbon atoms in the weakly fluorinated region (CxF, x ≥ 2), whereas the (C-F)I bonds cluster at the strongly deformed carbon framework with a F/C ratio of about 1. The thermostability of (C-F)II is lower than that of (C-F)I bonds. This is because the coplanar structure of the weakly fluorinated region tends to transform to the planar aromatic ring with the breaking of the C-F bond as compared with the strong fluorinated nonplanar region.

Controllable defluorination of fluorinated graphene and weakening of C-F bonding under the action of nucleophilic dipolar solvent.

The effect of solvent on the chemical structure and properties of fluorinated graphene (FG) was particularly investigated in this work. It is found that the reduction of FG and the weakening of strong covalent C-F bonding take place under the action of some dipolar solvents even at room temperature. The rate of the C-F bond rupture reaction is positively influenced by the dipole moment of solvent and fluorine coverage of FG sheets. Meanwhile, defluorination of FG is controllable through the time and temperature of solvent treatment. These solvents function as the nucleophilic catalysts, promoting chemical transformation, which leads to a series of changes in the structure and properties of FG, such as a decline of fluorine concentration of about 40% and the reduction of thermal stability and band gap from 3 to 2 eV. After the treatment with dipolar solvent N-methyl-2-pyrrolidinone, FG maintained a capacity of 255 mA h g(-1) and a power density of 2986 W kg(-1) at a high discharge rate, while the pristine FG could not be discharged at all. This is called the "solvent activation" effect on the electrochemical performance of FG. The finding may draw attention to the effect of various external factors on the chemical structure and properties of FG, which is of great importance for the realization of the FG's potential.