Customized Ultrathin Oxygen Vacancy-Rich Bi2W0.2Mo0.8O6 Nanosheets Enabling a Stepwise Charge Separation Relay and Exposure of Lewis Acid Sites toward Broad-Spectrum Photothermal Catalysis.

Designing robust photocatalysts with broad light absorption, effective charge separation, and sufficient reactive sites is critical for achieving efficient solar energy conversion. However, realizing these aims simultaneously through a single material modulation approach poses a challenge. Here, a 2D ultrathin oxygen vacancy (Ov)-rich Bi2W0.2Mo0.8O6 solid solution photocatalyst is designed and fabricated to tackle the dilemma through component and structure optimization. Specifically, the construction of a solid solution with ultrathin structure initially facilitates the separation of photoinduced electron-hole pairs, while the introduction of Ov strengthens such separation. In the meantime, the presence of Ov extends light absorption to the NIR region, triggering a photothermal effect that further enhances the charge separation and accelerates the redox reaction. As such, photoinduced charge carriers in the Ov-Bi2W0.2Mo0.8O6 are separated step by step via the synergistic action of 2D solid solution, OV, and solar heating. Furthermore, the introduction of OV exposes surface metal sites that serve as reactive Lewis acid sites, promoting the adsorption and activation of toluene. Consequently, the designed Ov-Bi2W0.2Mo0.8O6 reveals an enhanced photothermal catalytic toluene oxidation rate of 2445 µmol g-1 h-1 under a wide spectrum without extra heat input. The performance is 9.0 and 3.9 times that of Bi2WO6 and Bi2MoO6 nanosheets, respectively.

A Hydrogel Electrolyte with High Adaptability over a Wide Temperature Range and Mechanical Stress for Long-Life Flexible Zinc-Ion Batteries.

Flexible zinc-ion batteries have garnered significant attention in the realm of wearable technology. However, the instability of hydrogel electrolytes in a wide-temperature range and uncontrollable side reactions of the Zn electrode have become the main problems for practical applications. Herein, N,N-dimethylformamide (DMF) to design a binary solvent (H2O-DMF) is introduced and combined it with polyacrylamide (PAM) and ZnSO4 to synthesize a hydrogel electrolyte (denoted as PZD). The synergistic effect of DMF and PAM not only guides Zn2+ deposition on Zn(002) crystal plane and isolates H2O from the Zn anode, but also breaks the hydrogen bonding network between water to improve the wide-temperature range stability of hydrogel electrolytes. Consequently, the symmetric cell utilizing PZD can stably cycle over 5600 h at 0.5 mA cm- 2@0.5 mAh cm-2. Furthermore, the Zn//PZD//MnO2 full cell exhibits favorable wide-temperature range adaptability (for 16000 cycles at 3 A g-1 under 25 °C, 750 cycles with 98 mAh g-1 at 0.1 A g-1 under -20 °C) and outstanding mechanical properties (for lighting up the LEDs under conditions of pressure, bending, cutting, and puncture). This work proposes a useful modification for designing a high-performance hydrogel electrolyte, which provides a reference for investigating the practical flexible aqueous batteries.

Barbier Polymerization-Induced Emission towards Fully Substituted Polyethylene Analogues with Non-Traditional Intrinsic Luminescence.

The properties of polyethylene are highly dependent on the variety and quantity of substitutions. Generally, polyethylene can only be fully substituted with fluorine atoms, mainly e. g., polytetrafluoroethylene and nafion, because atomic radius of fluorine atom is small enough. The preparation of fully substituted polyethylene analogues (FSPEA) and their non-traditional intrinsic luminescence (NTIL) are attractive, especially for substitutions with relatively larger atomic radii than a fluorine atom. Here, Barbier polymerization-induced emission (PIE) is demonstrated as a universal method for the molecular design of NTIL type FSPEAs with intriguing aggregation-induced emission (AIE) behaviors. Through Barbier polymerization of diphenyldichloromethane and different peroxyesters in the presence of Mg in one pot, a series of FSPEAs, including polytriphenylethanol (PTPE), polydiphenylfurylethanol (PDPFE), polydiphenylthiophenylethanol (PDPTE) and polydiphenylnaphthylethanol (PDPNE) have been successfully prepared. Further potential applications for explosive detection, artificial light-harvesting system and white phosphor-converted light-emitting diode are investigated. Therefore, this work opens up a new approach for the molecular design of FSPEA with non-conjugated luminescence, which may cause inspirations to different research fields like polyolefin and luminescent materials.

Formation of Size-Controllable Tetragonal Nanoprisms by Crystallization-Directed Ionic Self-Assembly of Anionic Porphyrin and PEO-Containing Triblock Cationic Copolymer.

The creation of anisotropic nanostructures with precise size control is desirable for new properties and functions, but it is challenging for ionic self-assembly (ISA) because of the non-directional electrostatic interactions. Herein, the formation of size-controllable tetragonal nanoprisms is reported via crystallization-directed ionic self-assembly (CDISA) through evaporating a micellar solution on solid substrates. First, ISA is designed with a crystalline polyethylene oxide (PEO) containing cationic polymer poly(2-(2-guanidinoethoxy)ethyl methacrylate)-b-poly(ethyleneoxide)-b-poly(2-(2-guanidinoethoxy)-ethylmethacrylate) (PGn -PEO230 -PGn ) and an anionic 5,10,15,20-Tetrakis(4-sulfonatophenyl) porphyrin (TPPS) to form micelles in aqueous solution. The PG segments binds excessive TPPS with amplenet chargeto form hydrophilic corona, while the PEO segments are unprecedentedly dehydrated and tightly packed into cores. Upon naturally drying the micellar solution on a silicon wafer, PEO crystallizationdirects the micelles to aggregate into square nanoplates, which are further connected to nanoprisms. Length and width of the nanoprisms can be facilely tuned by varying the initial concentration. In this hierarchical process, the aqueous self-assembly is prerequisite and the water evaporation rate is crucial for the formation of nanostructures, which provides multiple factors for morphology regulating. Such precise size-control strategy is highly expected to provide a new vision for the design of advanced materials with size controllable anisotropic nanostructures.

Structure Engineering of BiSbSx Nanocrystals Embedded within Sulfurized Polyacrylonitrile Fibers for High Performance of Potassium-Ion Batteries.

Potassium-ion batteries (PIBs) are regarded as promising candidates in next-generation energy storage technology; however, the electrode materials in PIBs are usually restricted by the shortcomings of large volume expansion and poor cycling stability stemming from a high resistance towards diffusion and insertion of large-sized K ions. In this study, BiSbSx nanocrystals are rationally integrated with sulfurized polyacrylonitrile (SPAN) fibres through electrospinning technology with an annealing process. Such a unique structure, in which BiSbSx nanocrystals are embedded inside the SPAN fibre, affords multiple binding sites and a short diffusion length for K+ to realize fast kinetics. In addition, the molecular structure of SPAN features robust chemical interactions for stationary diffluent discharge products. Thus, the electrode demonstrates a superior potassium storage performance with an excellent reversible capacity of 790 mAh g-1 (at 0.1 A g-1 after 50 cycles) and 472 mAh g-1 (at 1 A g-1 after 2000 cycles). It's one of the best performances for metal dichalcogenides anodes for PIBs to date. The unusual performance of the BiSbSx @SPAN composite is attributed to the synergistic effects of the judicious nanostructure engineering of BiSbSx nanocrystals as well as the chemical interaction and confinement of SPAN fibers.

Unpredicted Concentration-Dependent Sensory Properties of Pyrene-Containing NBN-Doped Polycyclic Aromatic Hydrocarbons.

Pyrene molecules containing NBN-doped polycyclic aromatic hydrocarbons (PAHs) have been synthesized by a simple and efficient intermolecular dehydration reaction between 1-pyrenylboronic acid and aromatic diamine. Pyrene-B (o-phenylenediamine) with a five-membered NBN ring and pyrene-B (1,8-diaminonaphthalene) with a six-membered NBN ring show differing luminescence. Pyrene-B (o-phenylenediamine) shows concentration-dependent luminescence and enhanced emission after grinding at solid state. Pyrene-B (1,8-diaminonaphthalene) exhibits a turn-on type luminescence upon fluoride ion addition at lower concentration, as well as concentration-dependent stability. Further potential applications of Pyrene-B (o-phenylenediamine) on artificial light-harvesting film were demonstrated by using commercial NiR dye as acceptor.

Pt-Chitosan-TiO2 for Efficient Photocatalytic Hydrogen Evolution via Ligand-to-Metal Charge Transfer Mechanism under Visible Light.

The Pt-chitosan-TiO2 charge transfer (CT) complex was synthesized via the sol-gel and impregnation method. The synthesized photocatalysts were thoroughly characterized, and their photocatalytic activity were evaluated toward H2 production through water reduction under visible-light irradiation. The effect of the preparation conditions of the photocatalysts (the degree of deacetylation of chitosan, addition amount of chitosan, and calcination temperature) on the photocatalytic activity was discussed. The optimal Pt-10%DD75-T200 showed a H2 generation rate of 280.4 µmol within 3 h. The remarkable visible-light photocatalytic activity of Pt-chitosan-TiO2 was due to the CT complex formation between chitosan and TiO2, which extended the visible-light absorption and induced the ligand-to-metal charge transfer (LMCT). The photocatalytic mechanism of Pt-chitosan-TiO2 was also investigated. This paper outlines a new and facile pathway for designing novel visible-light-driven photocatalysts that are based on TiO2 modified by polysaccharide biomass wastes that are widely found in nature.

N-doped CoAl oxides from hydrotalcites with enhanced oxygen vacancies for excellent low-temperature propane oxidation.

A series of nitrogen-doped CoAlO (N-CoAlO) were constructed by a hydrothermal route combined with a controllable NH3 treatment strategy. The effects of NH3 treatment on the physico-chemical properties and oxidation activities of N-CoAlO catalysts were investigated. In comparison to CoAlO, a smallest content decrease in surface Co3+ (serving as active sites) while a largest increased amount of surface Co2+ (contributing to oxygen species) are obtained over N-CoAlO/4h among the N-CoAlO catalysts. Meanwhile, a maximum N doping is found over N-CoAlO/4h. As a result, N-CoAlO/4h (under NH3 treatment at 400°C for 4 hr) with rich oxygen vacancies shows optimal catalytic activity, with a T90 (the temperature required to reach a 90% conversion of propane) at 266°C. The more oxygen vacancies are caused by the co-operative effects of N doping and suitable reduction of Co3+ for N-CoAlO/4h, leading to an enhanced oxygen mobility, which in turn promotes C3H8 total oxidation activity dominated by Langmuir-Hinshelwood mechanism. Moreover, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTs) analysis shows that N doping facilities the decomposition of intermediate species (propylene and formate) into CO2 over the catalyst surface of N-CoAlO/4h more easily. Our reported design in this work will provide a promising way to develop abundant oxygen vacancies of Co-based catalysts derived from hydrotalcites by a simple NH3 treatment.

Amorphous Boron Dispersed in LaCoO3 with Large Oxygen Vacancies for Efficient Catalytic Propane Oxidation.

Unsatisfactory oxygen mobility is a considerable barrier to the development of perovskites for low-temperature volatile organic compounds (VOCs) oxidation. This work introduced small amounts of dispersed non-metal boron into the LaCoO3 crystal through an easy sol-gel method to create more oxygen defects, which are conducive to the catalytic performance of propane (C3 H8 ) oxidation. It reveals that moderate addition of boron successfully induces a high distortion of the LaCoO3 crystal, decreases the perovskite particle size, and produces a large proportion of bulk Co2+ species corresponding to abundant oxygen vacancies. Additionally, surface Co3+ species, as the acid sites, which are active for cleaving the C-H bonds of C3 H8 molecules, are enriched. As a result, the LCB-7 (molar ratio of Co/B=0.93:0.07) displays the best C3 H8 oxidation activity. Simultaneously, the above catalyst exhibits superior thermal stability against CO2 and H2 O, lasting 200 h. This work provides a new strategy for modifying the catalytic VOCs oxidation performance of perovskites by the regulation of amorphous boron dispersion.

Facile Synthesis of Ultra-Small Few-Layer Nanostructured MoSe2 Embedded on N, P Co-Doped Bio-Carbon for High-Performance Half/Full Sodium-Ion and Potassium-Ion Batteries.

Sodium/potassium-ion batteries (SIBs/PIBs) arouse intensive interest on account of the natural abundance of sodium/potassium resources, the competitive cost and appropriate redox potential. Nevertheless, the huge challenge for SIBs/PIBs lies in the scarcity of an anode material with high capacity and stable structure, which are capable of accommodating large-size ions during cycling. Furthermore, using sustainable natural biomass to fabricate electrodes for energy storage applications is a hot topic. Herein, an ultra-small few-layer nanostructured MoSe2 embedded on N, P co-doped bio-carbon is reported, which is synthesized by using chlorella as the adsorbent and precursor. As a consequence, the MoSe2 /NP-C-2 composite represents exceedingly impressive electrochemical performance for both sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs). It displays a promising reversible capacity (523 mAh g-1 at 100 mA g-1 after 100 cycles) and impressive long-term cycling performance (192 mAh g-1 at 5 A g-1 even after 1000 cycles) in SIBs, which are some of the best properties of MoSe2 -based anode materials for SIBs to date. To further probe the great potential applications, full SIBs pairing the MoSe2 /NP-C-2 composite anode with a Na3 V2 (PO4 )3 cathode also exhibits a satisfactory capacity of 215 mAh g-1 at 500 mA g-1 after 100 cycles. Moreover, it also delivers a decent reversible capacity of 131 mAh g-1 at 1 A g-1 even after 250 cycles for PIBs.

Preparation of a Si/SiO2 -Ordered-Mesoporous-Carbon Nanocomposite as an Anode for High-Performance Lithium-Ion and Sodium-Ion Batteries.

In this work, an Si/SiO2 -ordered-mesoporous carbon (Si/SiO2 -OMC) nanocomposite was initially fabricated through a magnesiothermic reduction strategy by using a two-dimensional bicontinuous mesochannel of SiO2 -OMC as a precursor, combined with an NaOH etching process, in which crystal Si/amorphous SiO2 nanoparticles were encapsulated into the OMC matrix. Not only can such unique porous crystal Si/amorphous SiO2 nanoparticles uniformly dispersed in the OMC matrix mitigate the volume change of active materials during the cycling process, but they can also improve electrical conductivity of Si/SiO2 and facilitate the Li+ /Na+ diffusion. When applied as an anode for lithium-ion batteries (LIBs), the Si/SiO2 -OMC composite displayed superior reversible capacity (958 mA h g-1 at 0.2 A g-1 after 100 cycles) and good cycling life (retaining a capacity of 459 mA h g-1 at 2 A g-1 after 1000 cycles). For sodium-ion batteries (SIBs), the composite maintained a high capacity of 423 mA h g-1 after 100 cycles at 0.05 A g-1 and an extremely stable reversible capacity of 190 mA h g-1 was retained even after 500 cycles at 1 A g-1 . This performance is one of the best long-term cycling properties of Si-based SIB anode materials. The Si/SiO2 -OMC composites exhibited great potential as an alternative material for both lithium- and sodium-ion battery anodes.

Recyclable and elastic highly thermally conductive epoxy-based composites with covalent-noncovalent interpenetrating networks.

High-power electronic architectures and devices require elastic thermally conductive materials. The use of epoxy resin in thermal management is limited due to its rigidity. Here, based on epoxy vitrimer, flexible polyethylene glycol (PEG) chains are introduced into covalent adaptable networks to construct covalent-noncovalent interpenetrating networks, enabling the elasticity of epoxy resins. Compared to traditional silicone-based thermal interface materials, the newly developed elastic epoxy resin shows the advantages of reprocessability, self-healing, and no small molecule release. Results show that, even after being filled with boron nitride and liquid metal, the material maintains its resilience, reprocessability and self-healing properties. Leveraging these characteristics, the composite can be further processed into thin films through a repeated pressing-rolling technique that facilitates the forced orientation of the fillers. Subsequently, the bulk composites are reconstructed using a film-stacking method. The results indicate that the thermal conductivity of the reconstructed bulk composite reaches 3.66 W m-1 K-1, achieving a 68% increase compared to the composite prepared through blending. Due to the existence of covalent adaptable networks, the inorganic and inorganic components of the composite prepared in this work can be completely separated under mild conditions, realizing closed-loop recycling.

The fate of plastic wraps in constructed wetland: Surface structure and microbial community.

The high use of plastic wraps leads to significant environmental pollution. In this study, the surface structure and microbial community evolution of commercially available plastic wraps [polyethylene (PE), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), and polylactic acid (PLA)] in constructed wetlands (CWs) were investigated. The results indicated that all plastic wraps gradually decreased in molecular weight, crystallinity, melting, and crystallization temperatures, whereas a gradual increase was observed in the surface roughness, polymer dispersity index (PDI), carbonyl index (CI) and Shannon index of microorganisms colonizing the CWs. The aging rate of the plastic wrap was in the order: PLA > PVC > PE > PVDC, at the same site in the CWs, and it was in the order: soil surface > plant roots > subsoil, for the same plastic wrap. The diversity of microorganisms colonizing the same plastic wrap was in the order: plant roots > subsoil > soil surface. The Shannon indices of microorganisms on plastic wraps were lower than those in the soil, indicating that the diversity of microorganisms colonizing plastic wraps is limited. Additionally, the microbial community structure on the plastic surface was co-differentiated by the plastic type, placement position in the CWs, and aging time. Significantly different microbial community structures were found on the PVC and PVDC wrap surfaces, revealing that the chlorine in plastics limits microbial diversity. Unclassified members of Rhizobiaceae and Pseudomonadaceae were the dominant genera on the surface of the plastic wraps, suggesting that they may be the microorganisms involved in plastic degradation processes. The study provides valuable perspectives to facilitate a comprehensive understanding of the migration, fate, and environmental risks associated with microplastics (MPs) in wetlands.

Chlorella filled poly(lactic acid) (PLA)/poly(butylene adipate-co-terephthalate) (PBAT) blend bio-composites compatible with additive manufacturing processes: Fluorescent and anti-counterfeiting QR codes applications.

Anti-counterfeiting in 3D printing has gained significant attention, however, current approaches often fall short of fully capitalizing on the inherent advantages of personalized manufacturing with this technology. Herein, we propose an embedded anti-counterfeiting scheme for additive manufacturing, accompanied by a novel fluorescent encrypted quick response (QR) method. This approach involves the development of a 3D printing filament utilizing poly(lactic acid) (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) bio-composites as the primary filament matrix, with varying quantities of Chlorella powder incorporated. The resulting filament has a good thermal stability near 200 °C and exhibits a distinctive red fluorescence under ultraviolet light, with the emission peak at 677 nm when excited by 415 nm blue light. Fluorescence imaging analysis confirms that the red fluorescence in 3D printed devices containing Chlorella is a result of the chlorophyll and its derivatives fluorescence effect. The fluorescent encrypted QR codes are inconspicuous in daylight but become easily discernible under ultraviolet light. In the cases of recognizable QR codes, the ∆Eab* values all exceed 35, and the LC/LB values deviate significantly from 1. This research delves into the fluorescence characteristics of Chlorella and highlights its applicability in 3D printing, specifically within the realm of product anti-counterfeiting, presenting a groundbreaking approach.

A Highly Sustainable Supramolecular Bioplastic Film with Superior Hydroplasticity and Biodegradability.

Massive accumulation of postconsumer plastic waste in eco-system has raised growing environmental concerns. Sustainable end-of-life managements of the indispensable plastic are highly demanding and challenging in modern society. To relieve the plastic menace, herein we present a full life cycle sustainable supramolecular bioplastic made from biomass-derived polyelectrolyte (chitosan quaternary ammonium salt, QCS) and natural sodium fatty acid (sodium laurate, SL) through solid-phase molecular self-assembly (SPMSA), by which the QCS-SL complexes, precipitated from mixing the aqueous solutions, self-assemble to form bioplastic film by mildly pressing at room temperature. The QCS-SL bioplastic films display superior hydroplasticity owing to the water-activated molecular rearrangement and electrostatic bond reconstruction, which allows facile self-healing and reprocessing at room temperature to significantly extend the service lifetime of both products and raw materials. With higher water content, the dynamic electrostatic interactions and precipitation-dissolution equilibrium endow the QCS-SL bioplastic films with considerable solubility in water, which is promising to mitigate the plastic accumulation in aquatic environment. Because both QCS and SL are biocompatible and biodegradable, the dissolved QCS-SL films are nontoxic and environmentally friendly. Thus, this novel supramolecular bioplastic is highly sustainable throughout the whole life cycle, which is expected to open a new vista in sustainable plastic materials.

Application of 3D printing technology for green synthesis of Fe2O3 using ABS/TPU/chlorella skeletons for methyl orange removal.

Photocatalysis is widely acknowledged as an efficient and environmentally friendly method for treating dye-contaminated wastewater. However, the utilization of powdered photocatalysts presents significant challenges, including issues related to recyclability and the potential for secondary pollution. Herein, a novel technique based on 3D printing for the synthesizing of iron oxide (Fe2O3) involving chlorella was presented. Initially, chlorella powders were immobilized within acrylonitrile butadiene styrene (ABS) and thermoplastic polyurethane (TPU) substrate plastics using melt extrusion technology. Subsequently, these composite materials were transformed into ABS/TPU/chlorella skeletons (ATCh40), through fused deposition molding (FDM) technology. The integration of Fe2O3 onto the ATCh40 (ATCh40-Fe2O3) skeletons was accomplished by subjecting them to controlled heating in an oil bath. A comprehensive characterization of the synthesized materials confirms the successful growth of Fe2O3 on the surface of 3D skeletons. This strategy effectively addresses the immobilization challenges associated with powdered photocatalysts. In photocatalytic degradation experiments targeting methyl orange (MO), the ATCh40-Fe2O3 skeletons exhibited a remarkable MO removal rate of 91% within 240 min. Under conditions where the pH of MO solution was maintained at 3, and the ATCh40-Fe2O3 skeletons were subjected to a heat treatment in a 150 °C blast drying oven for 2 hours, the degradation rate of MO remained substantial, achieving 90% removal after 6 cycles. In contrast, when the same synthetic procedure was applied to ABS/TPU (AT) skeletons, the resulting product was identified as α-FeOOH. The MO removal rate by the AT-α-FeOOH skeletons was considerably lower, reaching only 49% after 240 min. This research provided a practical approach for the construction of photocatalytic devices through the use of 3D printing technology.

Chitosan -NH2 derived efficient Co3O4 catalyst for styrene catalytic oxidation: Simultaneously regulating particle size and Co valence.

In this study, a Co3O4 catalyst is synthesised using the chitosan-assisted sol-gel method, which simultaneously regulates the grain size, Co valence and surface acidity of the catalyst through a chitosan functional group. The complexation of the free -NH2 complex inhibits particle agglomeration; thus, the average particle size of the catalyst decreases from 82 to 31 nm. Concurrently, Raman spectroscopy, hydrogen temperature-programmed reduction, electron paramagnetic resonance spectroscopy and X-ray photoelectron spectroscopy experiments demonstrate that doping with chitosan N sources effectively modulates Co2+ to promote the formation of oxygen vacancies. In addition, water washing after catalyst preparation can considerably improve the low-temperature (below 250 °C) activity of the catalyst and eliminate the side effects of alkali metal on catalyst activity. Moreover, the presence of Brønsted and Lewis acid sites promotes the adsorption of C8H8. Consequently, CS/Co3O4-W presents the highest catalytic oxidation activity for C8H8 at low temperatures (R250 °C = 8.33 µmol g-1 s-1, WHSV = 120,000 mL hr-1∙g-1). In situ DRIFTS and 18O2 isotope experiments demonstrate that the oxidation of the C8H8 reaction is primarily dominated by the Mars-van Krevelen mechanism. Furthermore, CS/Co3O4-W exhibits superior water resistance (1- and 2- vol% H2O), which has the potential to be implemented in industrial applications.

Microplastics as an emerging vector of Cr(VI) in water: Correlation of aging properties and adsorption behavior.

Microplastics (MPs) are emerging contaminants with growing concerns due to their potential adverse effects on the environment. However, understanding the aging properties and adsorption behavior of MPs is still limited. In this study, we investigated the correlation between the adsorption capacity, aging stages, and aging properties of polyethylene MPs using a correlation equation. Our results revealed that the trends of O/C ratio and contact angle of polyethylene MPs with aging time were fitted to be linear under xenon lamp accelerated aging conditions. Conversely, the trends of other properties such as particle size, crystallinity, and molecular weight with time were fitted to conform to the Boltzmann equation. Moreover, the aging curve data for carbonyl index and molecular weight (Mw) perfectly matched, confirming Mw play a crucial role in verifying the aging process. Additionally, the adsorption amount of polyethylene MPs increased sharply with the increase of aging ages, reaching up to 1.850 mg/g. The adsorption data fit well to the pseudo-second-order kinetics and Langmuir model, suggesting that the adsorption process is dominated by chemisorption. The low pH and low salt concentration is beneficial to the adsorption capacity of MPs onto Cr(VI). Further, a relationship equation was established to predict adsorption risk at different aging stages. These findings provide new insights into the impact of aging on pollutants transport and the fate of MPs, enabling the prediction of adsorption risk of MPs at different aging stages in water environments.

Visible-Light-Driven Photocatalytic Dehydrogenation of Alcohols on TiO2 via Ligand-to-Metal Charge Transfer for Coproduction of H2 and Aldehydes.

Developing visible-light-driven photocatalysts for the catalytic dehydrogenation of organics is of great significance for sustainable solar energy utilization. Here, we first report that aromatic alcohols could be efficiently split into H2 and aldehydes over TiO2 under visible-light irradiation through a ligand-to-metal charge transfer (LMCT) mechanism. A series of TiO2 catalysts with different surface contents of the hydroxyl group (-OH) have been synthesized by controlling the hydrothermal and calcination synthesis methods. An optimal H2 production rate of 18.6 µmol h-1 is obtained on TiO2 synthesized from the hydrothermal method with a high content of surface -OH. Experimental characterizations and comparison studies reveal that the surface -OH markedly influences the formation of LMCT complexes and thus changes the visible-light-driven photocatalytic performance. This work is anticipated to inspire further research endeavors in the design and fabrication of visible-light-driven photocatalyst systems based on the LMCT mechanism to realize the simultaneous synthesis of clean fuel and fine chemicals.

Surface Hydrophobization Provides Hygroscopic Supramolecular Plastics Based on Polysaccharides with Damage-Specific Healability and Room-Temperature Recyclability.

Supramolecular materials with room-temperature healability and recyclability are highly desired because they can extend materials lifetimes and reduce resources consumption. Most approaches toward healing and recycling rely on the dynamically reversible supramolecular interactions, such as hydrogen, ionic and coordinate bonds, which are hygroscopic and vulnerable to water. The general water-induced plasticization facilitates the healing and reprocessing process but cause a troubling problem of random self-adhesion. To address this issue, here it is reported that by modifying the hygroscopic surfaces with hydrophobic alkyl chains of dodecyltrimethoxysilane (DTMS), supramolecular plastic films based on commercial raw materials of sodium alginate (SA) and cetyltrimethylammonium bromide (CTAB) display extraordinary damage-specific healability. Owing to the hydrophobic surfaces, random self-adhesion is eliminated even under humid environment. When damage occurs, the fresh surfaces with ionic groups and hydroxyl groups expose exclusively at the damaged site. Thus, damage-specific healing can be readily facilitated by water-induced plasticization. Moreover, the films display excellent room-temperature recyclability. After multiple times of reprocessing and re-modifying with DTMS, the rejuvenated films exhibit fatigueless mechanical properties. It is anticipated that this approach to damage-specific healing and room-temperature recycling based on surface hydrophobization can be applied to design various of supramolecular plastic polysaccharides materials for building sustainable societies.