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.

Surface structures changes and biofilm communities development of degradable plastics during aging in coastal seawater.

Biodegradable plastics (BPs) are a suitable alternative to conventional plastics. Still, their excessive or unplanned use may disrupt the abundance and community structure of the microbial population. To this end, a 58-day experiment in which biodegradable plastic objects, such as bags and boxes, were exposed to near-coastal seawater was conducted. They also assessed how they affected the diversity and organization of bacterial populations in seawater and on the surface of BPs products. It is evident that after the exposure time, both BP's bag and box products deteriorate in the ocean to varying degrees. The results of high-throughput sequencing of bacterial communities in seawater and those colonized on BPs products reveal significant differences in microbial community structures between seawater and BPs plastic samples. These suggest that the degradation of biodegradable plastics is shadowed by microorganisms and exposure time, while BP products influence the structural characteristics of microbial communities.

Fabrication of Graphene-Modified Styrene-Acrylic Emulsion by In Situ Aqueous Polymerization.

With the aim of developing green coatings, styrene-acrylic emulsion has been widely used in architectural coatings due to its excellent environmental protection and energy conservation. Nevertheless, the lack of water and oxygen resistance of water-based styrofoam coatings has promoted various nanomaterials being studied for modification. To improve the performance of waterborne styrofoam coating, we introduced the graphene nanopowder and expected to enable it with the function of electromagnetic interference (EMI) shielding to reduce the damage of electromagnetic radiation. In this paper, the problem of poor interface compatibility between graphene and polymer resin was successfully addressed by in situ polymerization. In the process of pre-polymerization of styrene-acrylic emulsion monomer, graphene-modified styrene-acrylic emulsion was obtained by introducing graphene aqueous dispersion. The results showed that the styrene-acrylic emulsion with 4 wt% aqueous graphene dispersions exhibited the best dispersion stability, improved water and oxygen resistance, and the conductivity reached 1.89 × 10-2 S/cm. Then, the graphene-modified coating for building was prepared by using graphene-modified styrofoam emulsion. All the performance indexes of the coating are in line with the industry standards, and it still showed benign EMI shielding effect even when the graphene content was low. It is demonstrated that in situ polymerization technology and the application of graphene in resin coatings modification will promote the development of green coatings.

Non-Layered Te/In2 S3 Tunneling Heterojunctions with Ultrahigh Photoresponsivity and Fast Photoresponse.

A photodetector based on 2D non-layered materials can easily utilize the photogating effect to achieve considerable photogain, but at the cost of response speed. Here, a rationally designed tunneling heterojunction fabricated by vertical stacking of non-layered In2 S3 and Te flakes is studied systematically. The Te/In2 S3 heterojunctions possess type-II band alignment and can transfer to type-I or type-III depending on the electric field applied, allowing for tunable tunneling of the photoinduced carriers. The Te/In2 S3 tunneling heterojunction exhibits a reverse rectification ratio exceeding 104 , an ultralow forward current of 10-12 A, and a current on/off ratio over 105 . A photodetector based on the heterojunctions shows an ultrahigh photoresponsivity of 146 A W-1 in the visible range. Furthermore, the devices exhibit a response time of 5 ms, which is two and four orders of magnitude faster than that of its constituent In2 S3 and Te. The simultaneously improved photocurrent and response speed are attributed to the direct tunneling of the photoinduced carriers, as well as a combined mechanism of photoconductive and photogating effects. In addition, the photodetector exhibits a clear photovoltaic effect, which can work in a self-powered mode.

Selective Decomposition of Waste Rubber from the Shoe Industry by the Combination of Thermal Process and Mechanical Grinding.

A major challenge in waste rubber (WR) industry is achieving a high sol fraction and high molecular weight of recycled rubber at the same time. Herein, the WR from the shoe industry was thermo-mechanically ground via the torque rheometer. The effect of grinding temperature and filling rate were systematically investigated. The particle size distribution, structure evolution, and morphology of the recycled rubber were explored by laser particle size analyzer, Fourier transform infrared spectroscopy (FTIR), sol fraction analysis, gel permeation chromatography (GPC), differential scanning calorimeter (DSC), and scanning electron microscope (SEM). The results indicate that the thermo-mechanical method could reduce the particle size of WR. Moreover, the particle size distribution of WR after being ground can be described by Rosin's equation. The oxidation reaction occurs during thermal-mechanical grinding. With the increase of the grinding temperature and filling rate, the sol fraction of the recycled WR increases. It is also found that a high sol fraction (43.7%) and high molecular weight (35,284 g/mol) of reclaimed rubber could be achieved at 80 °C with a filling rate of 85%. Moreover, the obtained recycled rubber compound with SBR show a similar vulcanization characteristics to pure SBR. Our selective decomposition of waste rubber strategy opens up a new way for upgrading WR in shoe industry.

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.

Endowing Acceptable Mechanical Properties of Segregated Conductive Polymer Composites with Enhanced Filler-Matrix Interfacial Interactions by Incorporating High Specific Surface Area Nanosized Carbon Black.

Tuning the high properties of segregated conductive polymer materials (CPCs) by incorporating nanoscale carbon fillers has drawn increasing attention in the industry and academy fields, although weak interfacial interaction of matrix-filler is a daunting challenge for high-loading CPCs. Herein, we present a facile and efficient strategy for preparing the segregated conducting ultra-high molecular weight polyethylene (UHMWPE)-based composites with acceptable mechanical properties. The interfacial interactions, mechanical properties, electrical properties and electromagnetic interference (EMI) shielding effectiveness (SE) of the UHMWPE/conducting carbon black (CCB) composites were investigated. The morphological and Raman mapping results showed that UHMWPE/high specific surface area CCB (h-CCB) composites demonstrate an obviously interfacial transition layer and strongly interfacial adhesion, as compared to UHMWPE/low specific surface area CCB (l-CCB) composites. Consequently, the high-loading UHMWPE/h-CCB composite (beyond 10 wt% CCB dosage) exhibits higher strength and elongation at break than the UHMWPE/l-CCB composite. Moreover, due to the formation of a densely stacked h-CCB network under the enhanced filler-matrix interfacial interactions, UHMWPE/h-CCB composite possesses a higher EMI SE than those of UHMWPE/l-CCB composites. The electrical conductivity and EMI SE value of the UHMWPE/h-CCB composite increase sharply with the increasing content of h-CCB. The EMI SE of UHMWPE/h-CCB composite with 10 wt% h-CCB is 22.3 dB at X-band, as four times that of the UHMWPE/l-CCB composite with same l-CCB dosage (5.6 dB). This work will help to manufacture a low-cost and high-performance EMI shielding material for modern electronic systems.

Enhancement of Electromagnetic Interference Shielding Performance and Wear Resistance of the UHMWPE/PP Blend by Constructing a Segregated Hybrid Conductive Carbon Black-Polymer Network.

The low-percolation-threshold conductive networking structure is indispensable for the high performance and functionalization of conductive polymer composites (CPCs). In this work, conductive carbon black (CCB)-reinforced ultrahigh-molecular-weight polyethylene (UHMWPE)/polypropylene (PP) blend with tunable electrical conductivity and good mechanical properties was prepared using a high-speed mechanical mixing method and a compression-molded process. An interconnecting segregated hybrid CCB-polymer network is formed in electrically conductive UHMWPE/PP/CCB (UPC) composites. The UPC composites possess a dense conductive pathway at a low percolation threshold of 0.48 phr. The composite with 3 phr CCB gives an electrical conductivity value of 1.67 × 10-3 S/cm, 12 orders of magnitude higher than that of the polymeric matrix, suggesting that CCB improves both the electrical conductivity and electromagnetic interference shielding effectiveness (EMI SE) of the composite at the loading fraction over its percolation threshold. The composite with 15 phr CCB presents an absorption-dominated electromagnetic interference shielding effectiveness (EMI SE) as high as 27.29 dB at the X-band. The composite also presents higher tribological properties, mechanical properties, and thermal stability compared to the UP blend. This effort provides a simple and effective way for the mass fabrication of CPC materials with excellent performance.

Adsorption-desorption behavior of methylene blue onto aged polyethylene microplastics in aqueous environments.

In this study, polyethylene microplastics were artificially photoaged by xenon light. Experiments were then performed with methylene blue (MB) dye to compare the changes in the structure, properties, and adsorption-desorption behaviors of the aged and virgin polyethylene microplastics. The results showed that the aged polyethylene microplastics were hydrophilic with oxygen-containing functional groups, which enhanced the adsorption capacity of polyethylene for MB from 0.63 mg·g-1 to 8.12 mg·g-1. The adsorption isotherms changed from the Henry model (virgin polyethylene microplastics) to the Langmuir model (aged polyethylene microplastics), indicating that the partitioning function was gradually replaced by a single-layer covering during the adsorption process. In addition, 7% and 17.8% of the MB loaded onto the aged polyethylene microplastics was desorbed into water and a simulated intestinal fluid, respectively. These findings reveal that aged polyethylene microplastics can accumulate MB, thus posing potential risks to aqueous environments and biological tissues.

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.

Efficient Removal of Organic Contaminants from Aqueous Solution by Highly Compressible Reusable Three-Dimensional Printing Sponges.

Adsorption is considered to be one of the most effective and economically viable technologies for removing contaminants from the environment. However, the disadvantages of its high-cost complicated process and difficulty in efficient recycling limit its practical application. Herein, a thermoplastic elastomer-polyvinyl alcohol composite (LAY-FOMM 60) sponge three-dimensional structure (3D printing sponge) was fabricated by the fused filament fabrication combined with water erosion technique. The size and shape of the resultant sponge were tailored, and the batch of adsorption/desorption experiments of Rhodamine B (RhB) onto the sponge was performed. The results show that the adsorption of RhB on the 3D printing sponge was mainly via physical adsorption, and pseudo-second-order and Langmuir models exhibited good correlation with the adsorption kinetic and isotherm data, respectively. Thermodynamic parameters suggest that the adsorption is an endothermic and spontaneous process. It is worth to note that the adsorption/desorption efficiency can be raised by compression. This results in high efficiency and low cost for adsorption/desorption process and benefit for regeneration of the adsorbent. The adsorption capacity was maintained over 85% of the initial capacity after being used for five cycles. The approach provides a simple strategy for manufacturing customizable porous adsorbent materials that meet various water treatment requirements.

Dual carbon decorated germanium-carbon composite as a stable anode for sodium/potassium-ion batteries.

In the present work, we introduce a dual carbon accommodated structure in which germanium nanoparticles are encapsulated into an ordered mesoporous carbon matrix (Ge-CMK) and further coated with an amorphous carbon layer (Ge@C-CMK) through a nano-casting route followed by chemical vapor deposition (CVD) treatment. In the resultant Ge@C-CMK composite, the unique lane-like pore structure that cooperates with the amorphous carbon surface can not only mitigate the volume expansion of germanium particles, but also improve the electrical conductivity of germanium as well as facilitate Na+/K+ diffusion. When employed as the anode of sodium-ion batteries, the Ge@C-CMK electrode exhibits stable capacity as well as long-term cycling stability (a stable capacity of 176 mAh g-1 at 1 A g-1 after 5000 cycles). Furthermore, it also delivers a reversible capacity when used as the anode of potassium-ion batteries. This demonstrates that the Ge@C-CMK electrode possesses promising application potential as an alternative anode in sodium and potassium ion storage applications.

Preparation of Layered Polyethylene Oxide/rGO Composite: Flexible Lateral Heat Spreaders.

In this paper, high thermal conductive polyethylene oxide (PEO)/reduced graphene oxide (rGO) composite is prepared via large-scale green reduction. Flexible layered PEO/GO composites are pre-prepared in aqueous solution. It is demonstrated that PEO chains can form hydrogen bonds with GO. Being driven by hydrogen bonds, GO/PEO composites show homogeneous and lateral highly oriented structures, resulting in excellent mechanical properties. The pre-prepared composite films are large scale soaked into ascorbic acid solution. GO nanosheets in the matrix of the composites can be reduced by ascorbic acid. The results indicate that PEO chains can repair the damage of the films caused by the reduction process. Therefore, the films can maintain their original configuration and still keep excellent flexibility. By comparison, pristine GO films are totally destroyed when the same reduction is experienced. Due to the presence of PEO, the lateral highly oriented structure of the composite will not be damaged. After reduction, the thermal conductivity of the composite reaches to 12.03 W m-1 K-1 along the rGO nanosheet oriented direction.

Simultaneously enhanced mechanical properties and flame retardancy of UHMWPE with polydopamine-coated expandable graphite.

The potential prospect of expandable graphite (EG) in the development of polymer composites is severely limited by required large additions and poor interface compatibility with the polymer. Inspired by mussels, polydopamine (PDA) can be used as an effective interface modifier for EG to prepare ultra high molecular weight polyethylene (UHMWPE) composites with superior mechanical properties and high flame retardancy. The surface of expandable graphite (EG) was coated with a thin adhesive PDA film through self-polymerization of dopamine. The modified expandable graphite (EG@PDA) was combined with APP to prepare UHMWPE flame retardant composites. Compared with UHMWPE/APP/EG (with 20 wt% APP/EG), UHMWPE/APP/EG@PDA (with 20 wt% APP/EG@PDA) gives a decrement by 16.7% in limiting oxygen index, 29.7% in the peak of the heat release rate, 20.4% in total heat release and 49.3% in total smoke release, with an increment by 37% in tensile strength and 67.9% in elongation at break, respectively. It is suggested that the presence of PDA as an interface modifier can greatly improve the interfacial compatibility between EG and UHMWPE. Moreover, it can lead to forming more char residue and reducing the release of smoke particulates during combustion of the composites.

Largely enhanced thermal conductivity and thermal stability of ultra high molecular weight polyethylene composites via BN/CNT synergy.

In recent years, thermally conductive polymer-based composites have garnered significant attention due to their light weight and easy formation process. In this work, the thermal conductivity of ultra high molecular weight polyethylene (UPE) composites was improved through construction of a hybrid filler network of boron nitride sheets (BNs) and carbon nanotubes (CNTs) in the matrix via hot compression. The morphology, UPE aggregate structure, thermal conductivity, heat dissipation capacity and thermal stability of the UPE composites were investigated. The thermal conduction mechanism of the UPE composites was explored through simulations with Agari's semi-empirical formula. The results showed that the thermal conductivity of the UPE composite with 40 wt% BNs and 7 wt% CNTs was 2.38 W m-1 K-1, which was 495% higher than that of pure UPE, showing a synergistic effect between BNs and CNTs. The simulations with Agari's semi-empirical simulation suggested that increasing the CNT content contributed to synergistically assist BNs to form a better continuous and effective hybrid filler thermal network, thereby reducing phonon scattering and thermal resistance between BNs. In addition, UPE composites doped with BNs and CNTs presented better heat dissipation capacity and higher thermal stability as compared to that of pure UPE.

Intermetallic Hydrides as Zintl Phases: A(3)TtH(2) Compounds (A = Ca, Yb; Tt = Sn, Pb) and Their Structural Relationship to the Corresponding Oxides.

Shiny crystals of the isotypic title compounds are obtained in high yield from suitable proportions of AH(2), metal A, and Sn or Pb in welded Ta containers slowly cooled from 1100 degrees C. These were characterized by single-crystal X-ray diffraction for Ca(3)SnH(2) and Ca(3)PbH(2) (orthorhombic, Cmcm (No. 63), Z = 4, a = 8.866(1), 8.937(1) Å, b = 11.371(2), 11.470(2) Å, c = 5.220(1), 5.2551(7) Å, respectively). The structure contains distorted hcp layers of Ca(3)Tt between which hydrogen occupies all tetrahedral voids formed by Ca atoms. These tetrahedra share three edges to form double chains along the c axis that are separated by Tt atoms. Both calcium compounds are diamagnetic semiconductors, and the family can all be formulated in terms of oxidation states as Zintl phases (A(+2))(3)Tt(-4)(H(-))(2). Their structure may be derived from the hexagonal version of the cubic perovskitic Ca(3)SnO by distortions that split the octahedral site in the oxide into edge-sharing tetrahedral pairs.