Bio-Polyethylene and Polyethylene Biocomposites: An Alternative toward a Sustainable Future.

Polyethylene (PE), a highly prevalent non-biodegradable polymer in the field of plastics, presents a waste management issue. To alleviate this issue, bio-based PE (bio-PE), derived from renewable resources like corn and sugarcane, offers an environmentally friendly alternative. This review discusses various production methods of bio-PE, including fermentation, gasification, and catalytic conversion of biomass. Interestingly, the bio-PE production volumes and market are expanding due to the growing environmental concerns and regulatory pressures. Additionally, the production of PE and bio-PE biocomposites using agricultural waste as filler materials, highlights the growing demand for sustainable alternatives to conventional plastics. According to previous studies, addition of ≈50% defibrillated corn and abaca fibers into bio-PE matrix and a compatibilizer, results in the highest Young's modulus of 4.61 and 5.81 GPa, respectively. These biocomposites have potential applications in automotive, building construction, and furniture industries. Moreover, the advancement made in abiotic and biotic degradation of PE and PE biocomposites is elucidated to address their environmental impacts. Finally, the paper concludes with insights into the opportunities, challenges, and future perspectives in the sustainable production and utilization of PE and bio-PE biocomposites. In summary, production of PE and bio-PE biocomposites can contribute to a cleaner and sustainable future.

Synergistic Combination of Sb2Si2Te6 Additives for Enhanced Average ZT and Single-Leg Device Efficiency of Bi0.4Sb1.6Te3-based Composites.

Thermoelectric materials are highly promising for waste heat harvesting. Although thermoelectric materials research has expanded over the years, bismuth telluride-based alloys are still the best for near-room-temperature applications. In this work, a ≈38% enhancement of the average ZT (300-473 K) to 1.21 is achieved by mixing Bi0.4Sb1.6Te3 with an emerging thermoelectric material Sb2Si2Te6, which is significantly higher than that of most BiySb2-yTe3-based composites. This enhancement is facilitated by the unique interface region between the Bi0.4Sb1.6Te3 matrix and Sb2Si2Te6-based precipitates with an orderly atomic arrangement, which promotes the transport of charge carriers with minimal scattering, overcoming a common factor that is limiting ZT enhancement in such composites. At the same time, high-density dislocations in the same region can effectively scatter the phonons, decoupling the electron-phonon transport. This results in a ≈56% enhancement of the thermoelectric quality factor at 373 K, from 0.41 for the pristine sample to 0.64 for the composite sample. A single-leg device is fabricated with a high efficiency of 5.4% at ΔT = 164 K further demonstrating the efficacy of the Sb2Si2Te6 compositing strategy and the importance of the precipitate-matrix interface microstructure in improving the performance of materials for relatively low-temperature applications.

Ambient Degradation Anisotropy and Mechanism of van der Waals Ferroelectric NbOI2.

The spontaneous centrosymmetry-breaking and robust room-temperature ferroelectricity in niobium oxide dihalides spurs a flurry of explorations into its promising second-order nonlinear optical properties, and promises potential applications in nonvolatile electro-optical and optoelectronic devices. However, the ambient stability of the niobium oxide dihalides remains questionable, which overshadows their future development. In this work, the chemical degradation of NbOI2 is comprehensively investigated using combined chemical and optical microscopies in conjunction with spectroscopies. We unveil the highly anisotropic degradation kinetics of NbOI2 driven by the hydrolysis process of the unstable dangling iodine bonds dominantly on the (010) facet and progressing along the c axis. Knowing its degradation mechanism, the NbOI2 flake can then be stabilized by the hexagonal boron nitride encapsulation, which isolates the air moisture. These findings provide direct insights into the ambient instability of NbOI2, and they deliver possible solutions to circumvent this issue, which are essential for its practical integration in photonic and electronic devices.

Engineering High Voltage Aqueous Aluminum-Ion Batteries.

The energy transition to renewables necessitates innovative storage solutions beyond the capacities of lithium-ion batteries. Aluminum-ion batteries (AIBs), particularly their aqueous variants (AAIBs), have emerged as potential successors due to their abundant resources, electrochemical advantages, and eco-friendliness. However, they grapple with achieving their theoretical voltage potential, often yielding less than expected. This perspective article provides a comprehensive examination of the voltage challenges faced by AAIBs, attributing gaps to factors such as the aluminum reduction potential, hydrogen evolution reaction, and aluminum's inherent passivation. Through a critical exploration of methodologies, strategies, such as underpotential deposition, alloying, interface enhancements, tailored electrolyte compositions, and advanced cathode design, are proposed. This piece seeks to guide researchers in harnessing the full potential of AAIBs in the global energy storage landscape.

Tuning Main Group Element-based Metal-Organic Framework to Boost Electrocatalytic Nitrogen Reduction Under Ambient Conditions.

Main group element-based materials are emerging catalysts for ammonia (NH3 ) production via a sustainable electrochemical nitrogen reduction reaction (N2 RR) pathway under ambient conditions. However, their N2 RR performances are less explored due to the limited active behavior and unclear mechanism. Here, an aluminum-based defective metal-organic framework (MOF), aluminum-fumarate (Al-Fum), is investigated. As a proof of concept, the pristine Al-Fum MOF is synthesized by the solvothermal reaction process, and the defect engineering method namely solvent-assisted linker exchange, is applied to create the defective Al sites. The defective Al sites play an important role in ensuring the N2 RR activity for defective Al-Fum. It is found that only the defective Al-Fum enables stable and effective electrochemical N2 RR, in terms of the highest production rate of 53.9 µg(NH3 ) h-1 mgcat -1 (in 0.4 m K2 SO4 ) and the Faradaic efficiency of 73.8% (in 0.1 m K2 SO4 ) at -0.15 V vs reversible hydrogen electrode) under ambient conditions. Density functional theory calculations confirm that the N2 activation can be achieved on the defective Al sites. Such sites also allow the subsequent protonation process via the alternating associative mechanism. This defect characteristic gives the main group Al-based MOFs the ability to serve as promising electrocatalysts for N2 RR and other attractive applications.

Functionalizing Separator by Coating a Lithiophilic Metal for Dendrite-Free Anode-free Lithium Metal Batteries.

A stable anode-free lithium metal battery (AFLMB) is accomplished by the adoption of a facile fabricated amorphous antimony (Sb)-coated separator (SbSC). The large specific surface area of the separator elevates lithium (Li)-Sb alloy kinetic, improving Li wetting ability on pristine copper current collector (Cu). When tested with LiNi0.8 Mn0.1 Co0.1 O2 (NMC811) as cathode, the full cell with SbSC demonstrates low nucleation overpotential with compact, dendrite-free and homogeneous Li plating, and exhibits a notable lithium inventory retention rate (LIRR) of 99.8 % with capacity retention of 93.6 % after 60 cycles at 0.5 C-rate. Conversely, full cells containing pristine separator/Cu (i. e., SC) and pristine separator/Sb-coated current collector (i. e., SSbC) display poor cycling performances with low LIRRs. Density functional theory corroborates the nucleation behaviours observed during in-situ half-cell Li deposition. Functionalizing polymeric separator by metallic coating in AFLMB is a novel approach in improving the cycle life of an AFLMB by promoting homogeneous Li plating behavior. This innovative approach exemplifies a promising applicability for uniform Li-plating behavior to achieve a longer cycle life in AFLMB.

Unconventional polarization fatigue in van der Waals layered ferroelectric ionic conductor CuInP2S6.

Recent progress in two-dimensional ferroelectrics greatly expands the versatility and tunability in van der Waals heterostructure based electronics. However, the switching endurance issue that widely plagues conventional ferroelectrics in practical applications is hitherto unexplored for van der Waals layered ferroelectrics. Herein, we report the observation of unusual polarization fatigue behaviors in van der Waals layered CuInP2S6, which also possesses finite ionic conductivity at room temperature. The strong intertwinement of the short-range polarization switching and long-range ionic movement in conjunction with the van der Waals layered structure gives rise to unique morphological and polarization evolutions under repetitive electric cycles. With the help of concerted chemical, structural, lattice vibrational and dielectric analyses, we unravel the critical role of the synergy of ionic migration and surface oxidation on the anomalous polarization enhancement and the eventual polarization degradation. This work provides a general insight into the polarization fatigue characteristics in ionically-active van der Waals ferroelectrics and delivers potential solutions for the realization of fatigue-free capacitors.

Balanced NOx- and Proton Adsorption for Efficient Electrocatalytic NOx- to NH3 Conversion.

Electrocatalytic nitrate (NO3-)/nitrite (NO2-) reduction reaction (eNOx-RR) to ammonia under ambient conditions presents a green and promising alternative to the Haber-Bosch process. Practically available NOx- sources, such as wastewater or plasma-enabled nitrogen oxidation reaction (p-NOR), typically have low NOx- concentrations. Hence, electrocatalyst engineering is important for practical eNOx-RR to obtain both high NH3 Faradaic efficiency (FE) and high yield rate. Herein, we designed balanced NOx- and proton adsorption by properly introducing Cu sites into the Fe/Fe2O3 electrocatalyst. During the eNOx-RR process, the H adsorption is balanced, and the good NOx- affinity is maintained. As a consequence, the designed Cu-Fe/Fe2O3 catalyst exhibits promising performance, with an average NH3 FE of ∼98% and an average NH3 yield rate of 15.66 mg h-1 cm-2 under the low NO3- concentration (32.3 mM) of typical industrial wastewater at an applied potential of -0.6 V versus reversible hydrogen electrode (RHE). With low-power direct current p-NOR generated NOx- (23.5 mM) in KOH electrolyte, the Cu-Fe/Fe2O3 catalyst achieves an FE of ∼99% and a yield rate of 15.1 mg h-1 cm-2 for NH3 production at -0.5 V (vs RHE). The performance achieved in this study exceeds industrialization targets for NH3 production by exploiting two available low-concentration NOx- sources.

N-Type Thermoelectric AgBiPbS3 with Nanoprecipitates and Low Thermal Conductivity.

Thermoelectric sulfide materials are of particular interest due to the earth-abundant and cost-effective nature of sulfur. Here, we report a new n-type degenerate semiconductor sulfide, AgBiPbS3, which adopts a Fm3̅m structure with a narrow band gap of ∼0.32 eV. Despite the homogeneous distribution of elements at the scale of micrometer, Ag2S nanoprecipitates with dimensions of several nanometers were detected throughout the matrix. AgBiPbS3 exhibits a low room-temperature lattice thermal conductivity of 0.88 W m-1 K-1, owing to the intrinsic low lattice thermal conductivity of Ag2S and the effective scattering of phonons at nanoprecipitate boundaries. Moreover, compared to AgBiS2, AgBiPbS3 demonstrates a significantly improved weighted mobility of >16 cm2 V-1 s-1 at 300 K, leading to an enhanced PF of 1.6 µW cm-1 K-2 at 300 K. The superior electrical transport in AgBiPbS3 can be attributed to the high valley degeneracy of the L point (the conduction band minimum), which is contributed by the Pb s and Pb p orbitals. Further, Ga doping is found to be effective in modulating the Fermi levels of AgBiPbS3, leading to further enhancement of PF with a PFave of 2.7 µW cm-1 K-2 in the temperature range of 300-823 K. Consequently, a relatively high ZTave of 0.22 and a peak ZT of ∼0.4 at 823 K have been achieved in 3% Ga-doped AgBiPbS3, highlighting the potential of AgBiPbS3 as an n-type thermoelectric sulfide.

Unexpected doping effects on phonon transport in quasi-one-dimensional van der Waals crystal TiS3 nanoribbons.

Doping usually reduces lattice thermal conductivity because of enhanced phonon-impurity scattering. Here, we report unexpected doping effects on the lattice thermal conductivity of quasi-one-dimensional (quasi-1D) van der Waals (vdW) TiS3 nanoribbons. As the nanoribbon thickness reduces from ~80 to ~19 nm, the concentration of oxygen atoms has a monotonic increase along with a 7.4-fold enhancement in the thermal conductivity at room temperature. Through material characterizations and atomistic modellings, we find oxygen atoms diffuse more readily into thinner nanoribbons and more sulfur atoms are substituted. The doped oxygen atoms induce significant lattice contraction and coupling strength enhancement along the molecular chain direction while have little effect on vdW interactions, different from that doping atoms induce potential and structural distortions along all three-dimensional directions in 3D materials. With the enhancement of coupling strength, Young's modulus is enhanced while phonon-impurity scattering strength is suppressed, significantly improving the phonon thermal transport.

Oxygen Plasma Induced Nanochannels for Creating Bimetallic Hollow Nanocrystals.

Platinum-based metal catalysts are considered excellent converters in various catalytic reactions, particularly in fuel cell applications. The atomic structure at the nanocrystal surface and the metal interface both influence the catalytic performance, controlling the efficiency of the electrochemical reactions. Here we report the synthesis of Ag/Pt and Ag/Pd core/shell nanocrystals and insight into the formation mechanism of these bimetallic core/shell nanocrystals when undergoing oxygen plasma treatment. We carefully designed the oxidation treatment that determines the structural and compositional evolution. The accelerated oxidation-triggered diffusion of Ag toward the outer metal shell leads to the Kirkendall effect. After prolonged oxygen plasma treatment, most core/shell nanocrystals evolve into hollow spheres. At the same time, a minor fraction of the metal remains unchanged with a well-protected Ag core and a monocrystalline Pt or Pd shell. We hypothesize that the O2 plasma disturbs the Pt or Pd shell surface and introduces active O species that react with the diffused Ag from the inside out. Based on EDX elemental mapping, combined with several electron microscopic techniques, we deduced the formation mechanism of the hollow structures to be as follows: (I) the oxidation of Ag within the Pt or Pd lattice causes a disrupted crystal lattice of Pt or Pd; (II) nanochannels arise at the defect locations on the Pt or Pd shell; (III) the remaining Ag atoms pass through these nanochannels and leave a hollow crystal behind. Our findings deepen the understanding of interface dynamics of bimetallic nanostructured catalysts under an oxidative environment and unveil an alternative approach for catalyst pretreatment.

Partially Neutralized Polyacrylic Acid as an Efficient Binder for Aqueous Ceramic-Coated Separators for Lithium-Ion Batteries.

A partially neutralized polyacrylic acid (Pn-PAA) is used for coating sub-micron-sized α-alumina on a conventional microporous polyolefin separator, fabricating a ceramic-coated separator (CCS). Pn-PAA acts as a dispersant and binder by adsorbing itself on alpha(α)-alumina surfaces under acidic condition through the columbic interaction, providing a repulsive force to disperse fine alumina in aqueous suspension, and binds alumina strongly on plasma-treated separator through hydrogen bonding. This CCS shows favorable wettability in carbonate-based liquid electrolyte and ionic conduction due to the high hydrophilicity of Pn-PAA and alumina. With that, this study found that Pn-PAA-made-CCS yields a substantial adhesion strength of ~106 N/m with enhanced cycle stability, a specific capacity of 145.0 mAh/g after 200 cycles at 1 C at room temperature in half cells (LFP/Li metal).

Recent Advances in Metal-Organic Framework-Based Nanomaterials for Electrocatalytic Nitrogen Reduction.

The production of ammonia under moderate conditions is of environmental and sustainable importance. The electrochemical nitrogen reduction reaction (E-NRR) method has been intensively investigated in the recent decades. Nowadays, the further development of E-NRR is largely hindered by the lack of competent electrocatalysts. Metal-organic frameworks (MOFs) are considered as the next-generation catalysts for E-NRR, featuring their tailorable structures, abundant active sites and favorable porosity. To present a comprehensive review on both the fundamental and advanced development in MOFs catalyst-based E-NRR field, this paper first introduces the basic principles of E-NRR, including the reaction mechanism, major apparatus components, performance criteria, and ammonia detection protocols. Next, the synthesis and characterization methods for MOFs and their derivatives are discussed. In addition, a reaction mechanism study via density functional theory calculations is also presented. After that, the recent advancement of MOF-based catalysts in the E-NRR field as well as the modification approaches on MOFs for E-NRR optimization is elaborated. Finally, the current challenges and outlook of MOF catalyst-based E-NRR field are emphasized.

Integration of Metal-Organic Frameworks and Metals: Synergy for Electrocatalysis.

Electrocatalysis is a highly promising technology widely used in clean energy conversion. There is a continuing need to develop advanced electrocatalysts to catalyze the critical electrochemical reactions. Integrating metal active species, including various metal nanostructures (NSs) and atomically dispersed metal sites (ADMSs), into metal-organic frameworks (MOFs) leads to the formation of promising heterogeneous electrocatalysts that take advantage of both components. Among them, MOFs can provide support and protection for the active sites on guest metals, and the resulting host-guest interactions can synergistically enhance the electrocatalytic performance. In this review, three key concerns on MOF-metal heterogeneous electrocatalysts regarding the catalytic sites, conductivity, and catalytic stability are first presented. Then, rational integration strategies of MOFs and metals, including the integration of metal NSs via surface anchoring, space confining, and MOF coating, as well as the integration of ADMSs either with the metal nodes/linkers or within the pores of MOFs, along with their recent progress on synergistic cooperation for specific electrochemical reactions are summarized. Finally, current challenges and possible solutions in applying these increasingly concerned electrocatalysts are also provided.

[Research and Practice of Vehicle-mounted Mobile CT Based on Emergency Medical Rescue].

OBJECTIVE: In order to solve the problem of inadequate CT screening ability in emergency medical rescue in remote mountainous areas, high-altitude areas, other public health events and sudden natural disasters, a vehicle-mounted mobile CT suitable for emergency medical rescue is studied. METHODS: A vehicle chassis system suitable for long-distance transportation and a cabin system suitable for epidemic prevention and control was designed. A domestic 32-slice CT with small volume, light weight and high stability was selected to design a vehicle-mounted mobile CT suitable for emergency medical rescue. RESULTS: The high-performance vehicle-mounted mobile CT can provide rapid support, and provide large-scale screening, emergency medical rescue, a supplement to daily CT scanning in peacetime and wartime. CONCLUSIONS: The vehicle CT has high stability, fast scanning speed and high social and economic value.

Discordant Distortion in Cubic GeMnTe2 and High Thermoelectric Properties of GeMnTe2-x%SbTe.

GeMnTe2 adopts a cubic rock salt structure and is a promising mid-temperature thermoelectric material. The pair distribution function analysis of neutron total scattering data, however, indicates that GeMnTe2 is locally distorted from the ideal rock salt structure with Ge2+ cations being discordant and displaced ∼0.3 Å off the octahedron center. By alloying GeMnTe2 with SbTe, the carrier concentration can be tuned in GeMnTe2-x%SbTe (x = 15.1), leading to converged multiple broad valence bands and a high Seebeck coefficient of >200 µV K-1 from 300 to 823 K. The system exhibits a large density-of-state effective mass of >10 me and a high weighted mobility of 80 cm2 V-1 s-1, leading to a power factor of 15 µWcm-1 K-2 at 823 K. The composition GeMnTe2-15.1%SbTe exhibits very low lattice thermal conductivity of ∼0.5 Wm-1 K-1 at 823 K, attributed to the combination of off-centering cations in the rock salt structure, Ge/Mn positional disorder, dislocations, and abundant Ge-rich and Mn-rich nanoparticles. A ZT value of ∼1.5 can be achieved for GeMnTe2-15.1%SbTe with a ZTave of 0.96 in the temperature range of 400-823 K.

Intrinsic Interfacial Dynamic Engineering of Zincophilic Microbrushes via Regulating Zn Deposition for Highly Reversible Aqueous Zinc Ion Battery.

Aqueous rechargeable zinc ion batteries are promising efficient energy storage systems due to remarkable safety and satisfactory capacity. However, zinc metal anode instability including dendrite growth and side reactions severely hinders widespread applications. Herein, zincophilic microbrushes have been in situ anchored on zinc plates through simple freeze-drying and mild reduction of graphene oxide, successfully overcoming these thorny issues. By introducing suitable oxygen-containing groups, the microbrushes exhibit a good affinity for zinc ions, thereby providing sufficient depositing sites, promoting zinc plating and stripping during cycling, and suppressing side reactions. The delicate zincophilic microbrushes can not only function as protective layer to guide the deposition of zinc ions, but also act as high-speed pathways to redistribute the zinc ion flux for rapid kinetics. Consequently, the microbrushes-covered zinc anode displays long lifespan and good durability, whenever in symmetric cell or full battery tests. This work paves a feasible bridge to design advanced aqueous anodes by architecting both structures and compositions of metal coverings.

Ammonia Electrosynthesis with a Stable Metal-Free 2D Silicon Phosphide Catalyst.

Metal-free 2D phosphorus-based materials are emerging catalysts for ammonia (NH3 ) production through a sustainable electrochemical nitrogen reduction reaction route under ambient conditions. However, their efficiency and stability remain challenging due to the surface oxidization. Herein, a stable phosphorus-based electrocatalyst, silicon phosphide (SiP), is explored. Density functional theory calculations certify that the N2 activation can be realized on the zigzag Si sites with a dimeric end-on coordinated mode. Such sites also allow the subsequent protonation process via the alternating associative mechanism. As the proof-of-concept demonstration, both the crystalline and amorphous SiP nanosheets (denoted as C-SiP NSs and A-SiP NSs, respectively) are obtained through ultrasonic exfoliation processes, but only the crystalline one enables effective and stable electrocatalytic nitrogen reduction reaction, in terms of an NH3 yield rate of 16.12 µg h-1  mgcat. -1 and a Faradaic efficiency of 22.48% at -0.3 V versus reversible hydrogen electrode. The resistance to oxidization plays the decisive role in guaranteeing the NH3 electrosynthesis activity for C-SiP NSs. This surface stability endows C-SiP NSs with the capability to serve as appealing electrocatalysts for nitrogen reduction reactions and other promising applications.

Emerging p-Block-Element-Based Electrocatalysts for Sustainable Nitrogen Conversion.

Artificial nitrogen conversion reactions, such as the production of ammonia via dinitrogen or nitrate reduction and the synthesis of organonitrogen compounds via C-N coupling, play a pivotal role in the modern life. As alternatives to the traditional industrial processes that are energy- and carbon-emission-intensive, electrocatalytic nitrogen conversion reactions under mild conditions have attracted significant research interests. However, the electrosynthesis process still suffers from low product yield and Faradaic efficiency, which highlight the importance of developing efficient catalysts. In contrast to the transition-metal-based catalysts that have been widely studied, the p-block-element-based catalysts have recently shown promising performance because of their intriguing physiochemical properties and intrinsically poor hydrogen adsorption ability. In this Perspective, we summarize the latest breakthroughs in the development of p-block-element-based electrocatalysts toward nitrogen conversion applications, including ammonia electrosynthesis from N2 reduction and nitrate reduction and urea electrosynthesis using nitrogen-containing feedstocks and carbon dioxide. The catalyst design strategies and the underlying reaction mechanisms are discussed. Finally, major challenges and opportunities in future research directions are also proposed.

Bismuth-nickel bimetal nanosheets with a porous structure for efficient hydrogen production in neutral and alkaline media.

Active and durable electrocatalysts are very important for efficient and economically sustainable hydrogen generation via electrocatalytic water splitting. A bismuth-nickel (Bi-Ni) bimetal nanosheet with a mesoporous structure was prepared via a self-template electrochemical in situ process. The Bi-Ni catalyst required overpotentials of 56 mV and 183 mV at 10 mA cm-2 for the hydrogen evolution reaction (HER), which were close to that of commercial Pt/C in 1.0 M KOH and 1.0 M PBS (pH 7.0), respectively. The electrocatalyst maintained a steady current density during 20 h electrolysis in 1.0 M KOH and 1.0 M PBS (pH 7.0). Density functional theory (DFT) indicated that the alloying effect could induce charge transfer from the Bi atom to Ni atom and thus modulate the d-band centre of Bi-Ni nanosheets, which could efficiently accelerate H* conversion and H2 desorption at the Ni active site. This promotes the HER kinetics. By adopting the Bi84.8Ni15.2 alloy as the cathode to establish a full-cell (IrO2∥Bi84.8Ni15.2) for water splitting in 1.0 M KOH, the required cell voltage was 1.53 V to drive 10 mA cm-2, which was lower than that of the IrO2∥Pt/C electrolyzer (1.64 V@10 mA cm-2).