Microporous Materials in Polymer Electrolytes: The Merit of Order.

Solid-state batteries (SSBs) have garnered significant attention in the critical field of sustainable energy storage due to their potential benefits in safety, energy density, and cycle life. The large-scale, cost-effective production of SSBs necessitates the development of high-performance solid-state electrolytes. However, the manufacturing of SSBs relies heavily on the advancement of suitable solid-state electrolytes. Composite polymer electrolytes (CPEs), which combine the advantages of ordered microporous materials (OMMs) and polymer electrolytes, meet the requirements for high ionic conductivity/transference number, stability with respect to electrodes, compatibility with established manufacturing processes, and cost-effectiveness, making them particularly well-suited for mass production of SSBs. This review delineates how structural ordering dictates the fundamental physicochemical properties of OMMs, including ion transport, thermal transfer, and mechanical stability. The applications of prominent OMMs are critically examined, such as metal-organic frameworks, covalent organic frameworks, and zeolites, in CPEs, highlighting how structural ordering facilitates the fulfillment of property requirements. Finally, an outlook on the field is provided, exploring how the properties of CPEs can be enhanced through the dimensional design of OMMs, and the importance of uncovering the underlying "feature-function" mechanisms of various CPE types is underscored.

Degradation Mechanisms of Electrodes Promotes Direct Regeneration of Spent Li-Ion Batteries: A Review.

The rapid growth of electric vehicle use is expected to cause a significant environmental problem in the next few years due to the large number of spent lithium-ion batteries (LIBs). Recycling spent LIBs will not only alleviate the environmental problems but also address the challenge of limited natural resources shortages. While several hydro- and pyrometallurgical processes are developed for recycling different components of spent batteries, direct regeneration presents clear environmental, and economic advantages. The principle of the direct regeneration approach is restoring the electrochemical performance by healing the defective structure of the spent materials. Thus, the development of direct regeneration technology largely depends on the formation mechanism of defects in spent LIBs. This review systematically details the degradation mechanisms and types of defects found in diverse cathode materials, graphite anodes, and current collectors during the battery's lifecycle. Building on this understanding, principles and methodologies for directly rejuvenating materials within spent LIBs are outlined. Also the main challenges and solutions for the large-scale direct regeneration of spent LIBs are proposed. Furthermore, this review aims to pave the way for the direct regeneration of materials in discarded lithium-ion batteries by offering a theoretical foundation and practical guidance.

Charge-Dependent Crossover in Aqueous Organic Redox Flow Batteries Revealed Using Online NMR Spectroscopy.

Aqueous organic redox-flow batteries (AORFBs) are promising candidates for low-cost grid-level energy storage. However, their wide-scale deployment is limited by crossover of redox-active material through the separator membrane, which causes capacity decay. Traditional membrane permeability measurements do not capture all contributions to crossover in working batteries, including migration and changes in ion size and charge. Here we present a new method for characterizing crossover in operating AORFBs using online 1H NMR spectroscopy. By the introduction of a separate pump to decouple NMR and battery flow rates, this method opens a route to quantitative time-resolved monitoring of redox-flow batteries under real operating conditions. In this proof-of-concept study of a 2,6-dihydroxyanthraquinone (2,6-DHAQ)/ferrocyanide model system, we observed a doubling of the 2,6-DHAQ crossover during battery charging, which we attribute to migration effects. This new membrane testing methodology will advance our understanding of crossover and accelerate the development of improved redox-flow batteries.

Surface Functionalized MXenes for Wastewater Treatment-A Comprehensive Review.

Over 80% of wastewater worldwide is released into the environment without proper treatment. Whilst environmental pollution continues to intensify due to the increase in the number of polluting industries, conventional techniques employed to clean the environment are poorly effective and are expensive. MXenes are a new class of 2D materials that have received a lot of attention for an extensive range of applications due to their tuneable interlayer spacing and tailorable surface chemistry. Several MXene-based nanomaterials with remarkable properties have been proposed, synthesized, and used in environmental remediation applications. In this work, a comprehensive review of the state-of-the-art research progress on the promising potential of surface functionalized MXenes as photocatalysts, adsorbents, and membranes for wastewater treatment is presented. The sources, composition, and effects of wastewater on human health and the environment are displayed. Furthermore, the synthesis, surface functionalization, and characterization techniques of merit used in the study of MXenes are discussed, detailing the effects of a range of factors (e.g., PH, temperature, precursor, etc.) on the synthesis, surface functionalization, and performance of the resulting MXenes. Finally, the limits of MXenes and MXene-based materials as well as their potential future research directions, especially for wastewater treatment applications are highlighted.

Microwave- and Formaldehyde-Assisted Synthesis of Ag-Ag3PO4 with Enhanced Photocatalytic Activity for the Degradation of Rhodamine B Dye and Crude Oil Fractions.

The release of crude oil and water-soluble dyes into our marine environment is a major global problem. An efficient semiconductor Ag-Ag3PO4 photocatalyst was synthesized using formaldehyde as a reducing agent to form surface active Ag on Ag3PO4 under microwave radiation for heating, and its potential in destroying environmental pollutants has been examined. The diffuse reflectance spectroscopy of Ag-Ag3PO4 revealed an enhanced absorption in the visible light region. The rate of photocatalytic degradation of rhodamine B by Ag-Ag3PO4 was over 4-fold compared to Ag3PO4. The potential application of Ag-Ag3PO4 in oil spill remediation was also examined through photocatalytic degradation of benzene, n-hexane, and 1:1 v/v benzene/methanol crude oil-soluble fractions. UV-vis and gas chromatography-mass spectrometry analysis of the crude oil components after visible light irradiation showed excellent degradation. The photocatalytic efficiency enhancement of Ag-Ag3PO4 is attributed to the excellent electron trapping of silver nanoparticles deposited on the surface of Ag3PO4. This work will motivate future studies to develop recyclable visible light photocatalysts for many applications.

Facile and scalable synthesis of silicon nanowires from waste rice husk silica by the molten salt process.

Designing nanostructured silicon, such as in the form of nanoparticles, wires, and porous structures, for high-performance Li-ion electrodes, has progressed significantly. These approaches have largely overcome the capacity fading of silicon electrodes from volume expansion during lithiation/de-lithiation. However, they involve high costs, complex processes, and hazardous precursors. Herein, we propose an electrochemical fabrication of silicon nanowires from waste rice husks via a molten salt process based on electrodeoxidation. The addition of NiO as an electric conductor improved the production efficiency and created pores in the nanowires after washing. The electrically produced high-purity silicon yielded high capacity, and the nanowires provided sufficient free volume to accommodate silicon electrode expansion, resulting in improved cycle life. The converted silicon nanowires from the molten salt process will help develop sustainable energy storage materials.

A simple sensing of hazardous photo-induced superoxide anion radicals using a molecular probe in ZnO-Nanoparticles aqueous medium.

The generation of reactive oxygen species (ROS) during the photolysis of sunscreens and sun blockers poses consumer safety concerns while necessitating proper identification and quantitation of ROS species. Here, a colorimetric sensing approach has been developed based on a molecular probe (2,3-bis-(2-methoxy-4-nitro-5-sulfophenyl)-2-H-tetrazolium-5-carboxanilide (XTT) tetrazolium salt) to quantitatively measure the photo-induced superoxide anion radicals (O2.) generated from the photocatalysis of zinc oxide nanoparticles (ZnO-NPs) in aqueous solutions. Note that superoxide anion radicals are assumed to be the main reactive oxygen species (ROS) generated from such photocatalysis. The characterisation of ZnO-NPs before and after irradiation showed average particle sizes of 616.5 and 295.3 nm and ζ-potential values of 0 and -24.4 mV, respectively. It is hoped that this proposed protocol can be further developed to efficiently detect other ROS present in inorganic sun blockers and to optimize the utility of various sunscreen formulations.

Correction: Ahmad, I.A., et al. Non-Isothermal Crystallisation Kinetics of Carbon Black-Graphene-Based Multimodal-Polyethylene Nanocomposites. Nanomaterials, 2019, 9, 100.

In the published paper [¹], there was a typo error mistake in Equation (5), which was supposed to be expressed as " log Z t + n log t = log K T - m log Φ " instead of "log Zt + n log t = log KT - ml" [...].

Rational approach to guest confinement inside MOF cavities for low-temperature catalysis.

Geometric or electronic confinement of guests inside nanoporous hosts promises to deliver unusual catalytic or opto-electronic functionality from existing materials but is challenging to obtain particularly using metastable hosts, such as metal-organic frameworks (MOFs). Reagents (e.g. precursor) may be too large for impregnation and synthesis conditions may also destroy the hosts. Here we use thermodynamic Pourbaix diagrams (favorable redox and pH conditions) to describe a general method for metal-compound guest synthesis by rationally selecting reaction agents and conditions. Specifically we demonstrate a MOF-confined RuO2 catalyst (RuO2@MOF-808-P) with exceptionally high catalytic CO oxidation below 150 °C as compared to the conventionally made SiO2-supported RuO2 (RuO2/SiO2). This can be caused by weaker interactions between CO/O and the MOF-encapsulated RuO2 surface thus avoiding adsorption-induced catalytic surface passivation. We further describe applications of the Pourbaix-enabled guest synthesis (PEGS) strategy with tutorial examples for the general synthesis of arbitrary guests (e.g. metals, oxides, hydroxides, sulfides).

Non-Isothermal Crystallisation Kinetics of Carbon Black- Graphene-Based Multimodal-Polyethylene Nanocomposites.

The effect of carbon black (CB) and microwave-induced plasma graphene (g) on the crystallisation kinetics of the multimodal high-density polyethylene was studied under non-isothermal conditions. The non-isothermal crystallisation behaviour of the multimodal-high-density polyethylene (HDPE), containing up to 5 wt.% graphene, was compared with that of neat multimodal-HDPE and its carbon black based nanocomposites. The results suggested that the non-isothermal crystallisation behaviour of polyethylene (PE)-g nanocomposites relied significantly on both the graphene content and the cooling rate. The addition of graphene caused a change in the mechanism of the nucleation and the crystal growth of the multimodal-HDPE, while carbon black was shown to have little effect. Combined Avrami and Ozawa equations were shown to be effective in describing the non-isothermal crystallisation behaviour of the neat multimodal-HDPE and its nanocomposites. The mean activation energy barrier (ΔE), required for the transportation of the molecular chains from the melt state to the growing crystal surface, gradually diminished as the graphene content increased, which is attributable to the nucleating agent effect of graphene platelets. On the contrary, the synergistic effect resulting from the PE-CB nanocomposite decreased the ΔE of the neat multimodal-HDPE significantly at the lowest carbon black content.

Bottom-up Formation of Carbon-Based Structures with Multilevel Hierarchy from MOF-Guest Polyhedra.

Three-dimensional carbon-based structures have proven useful for tailoring material properties in structural mechanical and energy storage applications. One approach to obtain them has been by carbonization of selected metal-organic frameworks (MOFs) with catalytic metals, but this is not applicable to most common MOF structures. Here, we present a strategy to transform common MOFs, by guest inclusions and high-temperature MOF-guest interactions, into complex carbon-based, diatom-like, hierarchical structures (named for the morphological similarities with the naturally existing diatomaceous species). As an example, we introduce metal salt guests into HKUST-1-type MOFs to generate a family of carbon-based nano-diatoms with two to four levels of structural hierarchy. We report control of the morphology by simple changes in the chemistry of the MOF and guest, with implications for the formation mechanisms. We demonstrate that one of these structures has unique advantages as a fast-charging lithium-ion battery anode. The tunability of composition should enable further studies of reaction mechanisms and result in the growth of a myriad of unprecedented carbon-based structures from the enormous variety of currently available MOF-guest candidates.

Lithium-Sulfur Capacitors.

Although many existing hybrid energy storage systems demonstrate promising electrochemical performances, imbalances between the energies and kinetics of the two electrodes must be resolved to allow their widespread commercialization. As such, the development of a new class of energy storage systems is a particular challenge, since future systems will require a single device to provide both a high gravimetric energy and a high power density. In this context, we herein report the design of novel lithium-sulfur capacitors. The resulting asymmetric systems exhibited energy densities of 23.9-236.4 Wh kg-1 and power densities of 72.2-4097.3 W kg-1, which are the highest reported values for an asymmetric system to date. This approach involved the use of a prelithiated anode and a hybrid cathode material exhibiting anion adsorption-desorption in addition to the electrochemical reduction and oxidation of sulfur at almost identical rates. This novel strategy yielded both high energy and power densities, and therefore establishes a new benchmark for hybrid systems.

Semi-Interpenetrating Polymer Networks for Enhanced Supercapacitor Electrodes.

Conducting polymers show great promise as supercapacitor materials due to their high theoretical specific capacitance, low cost, toughness, and flexibility. Poor ion mobility, however, can render active material more than a few tens of nanometers from the surface inaccessible for charge storage, limiting performance. Here, we use semi-interpenetrating networks (sIPNs) of a pseudocapacitive polymer in an ionically conductive polymer matrix to decrease ion diffusion length scales and make virtually all of the active material accessible for charge storage. Our freestanding poly(3,4-ethylenedioxythiophene)/poly(ethylene oxide) (PEDOT/PEO) sIPN films yield simultaneous improvements in three crucial elements of supercapacitor performance: specific capacitance (182 F/g, a 70% increase over that of neat PEDOT), cycling stability (97.5% capacitance retention after 3000 cycles), and flexibility (the electrodes bend to a <200 µm radius of curvature without breaking). Our simple and controllable sIPN fabrication process presents a framework to develop a range of polymer-based interpenetrated materials for high-performance energy storage technologies.

Structure and photoluminescence properties of red-emitting apatite-type phosphor NaY9(SiO4)6O2:Sm3+ with excellent quantum efficiency and thermal stability for solid-state lighting.

A novel red-emitting phosphor NaY9(SiO4)6O2:Sm3+ (NYS:Sm3+) was synthesized and the X-ray diffraction and high-resolution TEM testified that the NYS compound belongs to the apatite structure which crystallized in a hexagonal unit cell with space group P63/m. The novel phosphor boasts of such three advantageous properties as perfect compatible match with the commercial UV chips, 73.2% quantum efficiency and 90.9% thermal stability at 150 °C. Details are as follows. NYS:Sm3+ phosphor showed obvious absorption in the UV regions centered at 407 nm, which can be perfectly compatible with the commercial UV chips. The property investigations showed that NYS:Sm3+ phosphor emitted reddish emission with CIE coordination of (0.563, 0.417). The optimum quenching concentration of Sm3+ in NYS phosphor was about 10%mol, and the corresponding concentration quenching mechanism was verified to be the electric dipole-dipole interaction. Upon excitation at 407 nm, the composition-optimized NYS:0.10Sm3+ exhibited a high quantum efficiency of 73.2%, and its luminescence intensity at 150 °C decreased simply to 90.9% of the initial value at room temperature. All of the results indicated that NYS:Sm3+ is a promising candidate as a reddish-emitting UV convertible phosphor for application in white light emitting diodes (w-LEDs).

Wafer-scale Fabrication of Non-Polar Mesoporous GaN Distributed Bragg Reflectors via Electrochemical Porosification.

Distributed Bragg reflectors (DBRs) are essential components for the development of optoelectronic devices. For many device applications, it is highly desirable to achieve not only high reflectivity and low absorption, but also good conductivity to allow effective electrical injection of charges. Here, we demonstrate the wafer-scale fabrication of highly reflective and conductive non-polar gallium nitride (GaN) DBRs, consisting of perfectly lattice-matched non-polar (11-20) GaN and mesoporous GaN layers that are obtained by a facile one-step electrochemical etching method without any extra processing steps. The GaN/mesoporous GaN DBRs exhibit high peak reflectivities (>96%) across the entire visible spectrum and wide spectral stop-band widths (full-width at half-maximum >80 nm), while preserving the material quality and showing good electrical conductivity. Such mesoporous GaN DBRs thus provide a promising and scalable platform for high performance GaN-based optoelectronic, photonic, and quantum photonic devices.

Rational Design of NiCoO2@SnO2 Heterostructure Attached on Amorphous Carbon Nanotubes with Improved Lithium Storage Properties.

It still remains very challenging to design proper heterostructures to enhance the electrochemical performance of transition metal oxide-based anode materials for lithium-ion batteries. Here, we synthesized the NiCoO2 nanosheets@SnO2 layer heterostructure supported by amorphous carbon nanotubes (ACNTs) which is derived from polymeric nanotubes (PNTs) by a stepwise method. The inner SnO2 layer not only provides a considerable capacity contribution but also produces the extra Li2O to promote the charge process of NiCoO2 and thus results in a rising cycling performance. Combining with the contribution of ACNTs backbone and ultrathin NiCoO2 nanosheets, the specific capacities of these one-dimensional nanostructures show an interesting gradually increasing trend even after 100 cycles at 400 mA g(-1) with a final result of 1166 mAh g(-1). This approach can be an efficient general strategy for the preparation of mixed-metal-oxide one-dimensional nanostructures and this innovative design of hybrid electrode materials provides a promising approach for batteries with improved electrochemical performance.

Reinforced Conductive Confinement of Sulfur for Robust and High-Performance Lithium-Sulfur Batteries.

Sulfur is an attractive cathode material in energy storage devices due to its high theoretical capacity of 1672 mAh g(-1). However, practical application of lithium-sulfur (Li-S) batteries can be achieved only when the major barriers, including the shuttling effect of polysulfides (Li2Sx, x = 3-8), significant volume change (∼80%), and the resultant rapid deterioration of electrodes, are tackled. Here, we propose an "inside-out" synthesis strategy by mimicking the structure of the pomegranate fruit to achieve conductive confinement of sulfur to address these issues. In the proposed pomegranate-like structure, sulfur and carbon nanotubes composite is encapsulated by the in situ formed amorphous carbon network, which allows the regeneration of electroactive material sulfur and the confinement of the sulfur as well as the lithium polysulfide within the electrical conductive carbon network. Consequently, a highly robust sulfur cathode is obtained, delivering remarkable performance in a Li-S battery. The obtained composite cathode shows a reversible capacity of 691 mAh g(-1) after 200 cycles with impressive cycle stability at the current density of 1600 mA g(-1).

Extraction of Mg(OH)2 from Mg silicate minerals with NaOH assisted with H2O: implications for CO2 capture from exhaust flue gas.

The utilisation of Mg(OH)2 to capture exhaust CO2 has been hindered by the limited availability of brucite, the Mg(OH)2 mineral in natural deposits. Our previous study demonstrated that Mg(OH)2 can be obtained from dunite, an ultramafic rock composed of Mg silicate minerals, in highly concentrated NaOH aqueous systems. However, the large quantity of NaOH consumed was considered an obstacle for the implementation of the technology. In the present study, Mg(OH)2 was extracted from dunite reacted in solid systems with NaOH assisted with H2O. The consumption of NaOH was reduced by 97% with respect to the NaOH aqueous systems, maintaining a comparable yield of Mg(OH)2 extraction, i.e. 64.8-66%. The capture of CO2 from a CO2-N2 gas mixture was tested at ambient conditions using a Mg(OH)2 aqueous slurry. Mg(OH)2 almost fully dissolved and reacted with dissolved CO2 by forming Mg(HCO3)2 which remained in equilibrium storing the CO2 in the aqueous solution. The CO2 balance of the process was assessed from the emissions derived from the power consumption for NaOH production and Mg(OH)2 extraction together with the CO2 captured by Mg(OH)2 derived from dunite. The process resulted as carbon neutral when dunite is reacted at 250 °C for durations of 1 and 3 hours and CO2 is captured as Mg(HCO3)2.

Synthesis of semiconducting polymer microparticles as solid ionophore with abundant complexing sites for long-life Pb(II) sensors.

Intrinsically electrically semiconducting microparticles of semiladder poly(m-phenylenediamine-co-2-hydroxy-5-sulfonic aniline) structures containing abundant functional groups, like -NH-, -N=, -NH2, -OH, -SO3H as complexation sites, were efficiently synthesized by chemical oxidative copolymerization of m-phenylenediamine and 2-hydroxy-5-sulfonic aniline. The obtained copolymers were found to be nonporous spherical microparticles that were able to achieve greater π-conjugated structure, smaller particle aggregate size, and stronger interaction with Pb(II) ions than poly(m-phenylenediamine) containing only -NH-, -N=, and -NH2. A potentiometric Pb(II) sensor was fabricated on the basis of the copolymer microparticles as a crucial solid ionophore component within plasticized PVC. The sensor exhibited a Nernstian response to Pb(II) ions over a wide concentration range, together with a fast response, a wide pH range capability, a long lifetime of up to 5 months, and good selectivity over a wide variety of other ions and redox species. The process for synthesizing the microparticles and fabricating the Pb(II)-sensor can be facilely scaled-up for use in the straightforward long-term online monitoring of Pb(II) ions in heavily polluted wastewaters. This study develops an understanding of the facile synthesis of conducting microparticles bearing many functional groups and their structures governing the potentiometric susceptibility toward interaction between Pb(II) ions and the microparticles for fabricating robust long-lived Pb(II)-sensor, signifying the potential suitability of such novel materials for inexpensive sensitive detection of Pb(II) ions.

Binder free three-dimensional sulphur/few-layer graphene foam cathode with enhanced high-rate capability for rechargeable lithium sulphur batteries.

A novel ultra-lightweight three-dimensional (3-D) cathode system for lithium sulphur (Li-S) batteries has been synthesised by loading sulphur on to an interconnected 3-D network of few-layered graphene (FLG) via a sulphur solution infiltration method. A free-standing FLG monolithic network foam was formed as a negative of a Ni metallic foam template by CVD followed by etching away of Ni. The FLG foam offers excellent electrical conductivity, an appropriate hierarchical pore structure for containing the electro-active sulphur and facilitates rapid electron/ion transport. This cathode system does not require any additional binding agents, conductive additives or a separate metallic current collector thus decreasing the weight of the cathode by typically ∼20-30 wt%. A Li-S battery with the sulphur-FLG foam cathode shows good electrochemical stability and high rate discharge capacity retention for up to 400 discharge/charge cycles at a high current density of 3200 mA g(-1). Even after 400 cycles the capacity decay is only ∼0.064% per cycle relative to the early (e.g. the 5th cycle) discharge capacity, while yielding an average columbic efficiency of ∼96.2%. Our results indicate the potential suitability of graphene foam for efficient, ultra-light and high-performance batteries.