Structural Electromagnetic Absorber Based on MoS2 /PyC-Al2 O3 Ceramic Metamaterials.

Limited by the types of suitable absorbents as well as the challenges in engineering the nanostructures (e.g., defects, dipoles, and hetero-interface) using state-of-the-art additive manufacturing (AM) techniques, the electromagnetic (EM) wave absorption performance of the current ceramic-based materials is still not satisfying. Moreover, because of the high residual porosity and the possible formation of cracks during sintering or pyrolysis, AM-formed ceramic components may in many cases exhibit low mechanical strength. In this work, semiconductive MoS2 and conductive PyC modified Al2 O3 (MoS2 /PyC-Al2 O3 ) ceramic-based structural EM metamaterials are developed by innovatively harnessing AM, precursor infiltration and pyrolysis (PIP), and hydrothermal methods. Three different meta-structures are successfully created, and the ceramic-based nanocomposite benefit from its optimization of EM parameters. Ultra-broad effective absorption bandwidth (EAB) of 35 GHz is achieved by establishment of multi-loss mechanism via nanostructure engineering and fabrication of meta-structures via AM. Due to the strengthening by the PyC phase, the bending strength of the resulting ceramics can reach ≈327 MPa, which is the highest value measured on 3D-printed ceramics of this type that has been reported so far. For the first time, the positive effect deriving from the engineering of the microscopic nano/microstructure and of the macroscopic meta-structure of the absorber on the permittivity and EM absorption performance is proposed. Integration of outstanding mechanical strength and ultra-broad EAB is innovatively realized through a multi-scale design route. This work provides new insights for the design of advanced ceramic-based metamaterials with outstanding performance under extreme environment.

A Novel High-Pressure Tin Oxynitride Sn2 N2 O.

We report the first oxynitride of tin, Sn2 N2 O (SNO), exhibiting a Rh2 S3 -type crystal structure with space group Pbcn. All Sn atoms are in six-fold coordination, in contrast to Si in silicon oxynitride (Si2 N2 O) and Ge in the isostructural germanium oxynitride (Ge2 N2 O), which appear in four-fold coordination. SNO was synthesized at 20 GPa and 1200-1500 °C in a large volume press. The recovered samples were characterized by synchrotron powder X-ray diffraction and single-crystal electron diffraction in the TEM using the automated diffraction tomography (ADT) technique. The isothermal bulk modulus was determined as Bo =193(5) GPa by using in-situ synchrotron X-ray diffraction in a diamond anvil cell. The structure model is supported by DFT calculations. The enthalpy of formation, the bulk modulus, and the band structure have been calculated.

Effect of the Content and Ordering of the sp2 Free Carbon Phase on the Charge Carrier Transport in Polymer-Derived Silicon Oxycarbides.

The present work elaborates on the correlation between the amount and ordering of the free carbon phase in silicon oxycarbides and their charge carrier transport behavior. Thus, silicon oxycarbides possessing free carbon contents from 0 to ca. 58 vol.% (SiOC/C) were synthesized and exposed to temperatures from 1100 to 1800 °C. The prepared samples were extensively analyzed concerning the thermal evolution of the sp2 carbon phase by means of Raman spectroscopy. Additionally, electrical conductivity and Hall measurements were performed and correlated with the structural information obtained from the Raman spectroscopic investigation. It is shown that the percolation threshold in SiOC/C samples depends on the temperature of their thermal treatment, varying from ca. 20 vol.% in the samples prepared at 1100 °C to ca. 6 vol.% for the samples annealed at 1600 °C. Moreover, three different conduction regimes are identified in SiOC/C, depending on its sp2 carbon content: (i) at low carbon contents (i.e., <1 vol.%), the silicon oxycarbide glassy matrix dominates the charge carrier transport, which exhibits an activation energy of ca. 1 eV and occurs within localized states, presumably dangling bonds; (ii) near the percolation threshold, tunneling or hopping of charge carriers between spatially separated sp2 carbon precipitates appear to be responsible for the electrical conductivity; (iii) whereas above the percolation threshold, the charge carrier transport is only weakly activated (Ea = 0.03 eV) and is realized through the (continuous) carbon phase. Hall measurements on SiOC/C samples above the percolation threshold indicate p-type carriers mainly contributing to conduction. Their density is shown to vary with the sp2 carbon content in the range from 1014 to 1019 cm-3; whereas their mobility (ca. 3 cm2/V) seems to not depend on the sp2 carbon content.

Carbon substitution for oxygen in silicates in planetary interiors.

Amorphous silicon oxycarbide polymer-derived ceramics (PDCs), synthesized from organometallic precursors, contain carbon- and silica-rich nanodomains, the latter with extensive substitution of carbon for oxygen, linking Si-centered SiO(x)C(4-x) tetrahedra. Calorimetric studies demonstrated these PDCs to be thermodynamically more stable than a mixture of SiO2, C, and silicon carbide. Here, we show by multinuclear NMR spectroscopy that substitution of C for O is also attained in PDCs with depolymerized silica-rich domains containing lithium, associated with SiO(x)C(4-x) tetrahedra with nonbridging oxygen. We suggest that significant (several percent) substitution of C for O could occur in more complex geological silicate melts/glasses in contact with graphite at moderate pressure and high temperature and may be thermodynamically far more accessible than C for Si substitution. Carbon incorporation will change the local structure and may affect physical properties, such as viscosity. Analogous carbon substitution at grain boundaries, at defect sites, or as equilibrium states in nominally acarbonaceous crystalline silicates, even if present at levels at 10-100 ppm, might form an extensive and hitherto hidden reservoir of carbon in the lower crust and mantle.

Surface-initiated anionic polymerization of [1]silaferrocenophanes for the preparation of colloidal preceramic materials.

A novel strategy for the preparation of poly(ferrocenylsilane) (PFS) immobilized on the surface of cross-linked polystyrene (PS) nanoparticles is reported. The ferrocene-containing core/shell architectures are shown to be excellent candidates as preceramic polymers yielding spherical ceramic materials consisting of iron silicide (Fe3 Si) and metallic iron after thermal treatment. For this purpose, dimethyl- and hydromethyl[1]silaferrocenophane monomers are polymerized by surface-initiated ring-opening polymerization upon taking advantage of residual vinylic moieties at the PS particle surface. A strategy for selective chain growth from the particle surface is developed without the formation of free PFS homopolymer in solution. The grafted particles are characterized using transmission electron microscopy (TEM) and dynamic light scattering (DLS). These particles are excellent precursors for ceramics as studied by thermogravimetric analysis (TGA). The composition of the ceramics is studied using X-ray diffraction (XRD) measurements, while the morphology is probed by scanning electron microscopy (SEM) revealing the original spherical shape of the precursor particles. Obtained ceramic materials- predominantly based on iron silicides-show ferromagnetic behavior as investigated by superconducting quantum interference device (SQUID) magnetization measurements at different temperatures.

High pressure synthesis of marcasite-type rhodium pernitride.

Marcasite-type rhodium nitride was successfully synthesized in a direct chemical reaction between a rhodium metal and molecular nitrogen at 43.2 GPa using a laser-heated diamond-anvil cell. This material shows a low zero-pressure bulk modulus of K0 = 235(13) GPa, which is much lower than those of other platinum group nitrides. This finding is due to the weaker bonding interaction between metal atoms and quasi-molecular dinitrogen units in the marcasite-type structure, as proposed by theoretical studies.

Single-source-precursor synthesis of hafnium-containing ultrahigh-temperature ceramic nanocomposites (UHTC-NCs).

Amorphous SiHfBCN ceramics were prepared from a commercial polysilazane (HTT 1800, AZ-EM), which was modified upon reactions with Hf(NEt2)4 and BH3·SMe2, and subsequently cross-linked and pyrolyzed. The prepared materials were investigated with respect to their chemical and phase composition, by means of spectroscopy techniques (Fourier transform infrared (FTIR), Raman, magic-angle spinning nuclear magnetic resonance (MAS NMR)), as well as X-ray diffraction (XRD) and transmission electron microscopy (TEM). Annealing experiments of the SiHfBCN samples in an inert gas atmosphere (Ar, N2) at temperatures in the range of 1300-1700 °C showed the conversion of the amorphous materials into nanostructured UHTC-NCs. Depending on the annealing atmosphere, HfC/HfB2/SiC (annealing in argon) and HfN/Si3N4/SiBCN (annealing in nitrogen) nanocomposites were obtained. The results emphasize that the conversion of the single-phase SiHfBCN into UHTC-NCs is thermodynamically controlled, thus allowing for a knowledge-based preparative path toward nanostructured ultrahigh-temperature stable materials with adjusted compositions.

Recycling and Reusing of Graphite from Retired Lithium-ion Batteries: A Review.

The proliferation of rechargeable lithium-ion batteries (LIBs) over the past decade has led to a significant increase in the number of electric vehicles (EVs) powered by these batteries reaching the end of their lifespan. With retired EVs becoming more prevalent, recycling and reusing their components, particularly graphite, has become imperative as the world transitions toward electric mobility. Graphite constitutes ≈20% of LIBs by weight, making it a valuable resource to be conserved. This review presents an in-depth analysis of the current global graphite mining landscape and explores potential opportunities for the "second life" of graphitefrom depleted LIBs. Various recycling and reactivation technologies in both industry and academia are discussed, along with potential applications for recycled graphite forming a vital aspect of the waste management hierarchy. Furthermore, this review addresses the future challenges faced by the recycling industry in dealing with expired LIBs, encompassing environmental, economic, legal, and regulatory considerations. In conclusion, this review provides a comprehensive overview of the developments in recycling and reusing graphite from retired LIBs, offering valuable insights for forthcoming large-scale recycling efforts.

Crystal structures of two new high-pressure oxynitrides with composition SnGe4N4O4, from single-crystal electron diffraction.

SnGe4N4O4 was synthesized at high pressure (16 and 20 GPa) and high temperature (1200 and 1500°C) in a large-volume press. Powder X-ray diffraction experiments using synchrotron radiation indicate that the derived samples are mixtures of known and unknown phases. However, the powder X-ray diffraction patterns are not sufficient for structural characterization. Transmission electron microscopy studies reveal crystals of several hundreds of nanometres in size with different chemical composition. Among them, crystals of a previously unknown phase with stoichiometry SnGe4N4O4 were detected and investigated using automated diffraction tomography (ADT), a three-dimensional electron diffraction method. Via ADT, the crystal structure could be determined from single nanocrystals in space group P63mc, exhibiting a nolanite-type structure. This was confirmed by density functional theory calculations and atomic resolution scanning transmission electron microscopy images. In one of the syntheses runs a rhombohedral 6R polytype of SnGe4N4O4 could be found together with the nolanite-type SnGe4N4O4. The structure of this polymorph was solved as well using ADT.

Visible light photocatalysis with c-WO(3-x)/WO3×H2O nanoheterostructures in situ formed in mesoporous polycarbosilane-siloxane polymer.

In recent years, there have been significant efforts to find novel photocatalytic materials with improved properties. Thus, there is an active ongoing search for new materials that can operate at a broad range of wavelengths for photocatalytic reactions. Among photocatalytically active semiconductors, considerable attention has been given to tungsten oxide with a band gap of E(g) ≈ 2.6 eV, which provides the opportunity to harvest visible light. In the present work, we report on a one-step synthesis of c-WO(3-x)/WO3×H2O nanowhiskers dispersed in a hydrolytically stable mesoporous polycarbosilane-siloxane ([-Si(O)CH2-]n) matrix. The as-synthesized nanocomposites possess high photocatalytic activity for the degradation of methylene blue (MB) under visible light irradiation. The enhanced photocatalytic activity is due to (i) the reduction in the electron-hole recombination rate because of the reduced dimensions of nanowhiskers, (ii) more efficient consumption of photogenerated electrons and holes as a result of the high surface-to-bulk-ratio of the nanowhiskers, and (iii) better electron-hole pair separation due to the formation of c-WO(3-x)/WO3×H2O nanoheterostructures.

Possible superhardness of CrB4.

Chromium tetraboride [orthorhombic, space group Pnnm (No. 58), a = 474.65(9) pm, b = 548.0(1) pm, c = 286.81(5) pm, and R value (all data) = 0.041], formerly described in space group Immm, was found not to be superhard, despite several theory-based prognoses. CrB(4) shows an almost temperature-independent paramagnetism, consistent with low-spin Cr(I) in a metallic compound. Conductivity measurements confirm the metallic character.

Silicon-containing polymer-derived ceramic nanocomposites (PDC-NCs): preparative approaches and properties.

Composites consist by definition of at least two materials (Gibbsian phases) with rather different properties. They exhibit a heterogeneous microstructure and possess improved properties with respect to their components. Furthermore, the design of their microstructure allows for tailoring their overall properties. In the last decades, intense work was performed on the synthesis of nanocomposites, which have the feature that at least one of their components is nanoscaled. However, the microstructure-property relationship of nanocomposite materials is still a challenging topic. This tutorial review paper deals with a special class of nanocomposites, i.e. polymer-derived ceramic nanocomposites (PDC-NCs), which have been shown to be promising materials for various structural and functional applications. Within this context, different preparative approaches for PDC-NCs as well as some of their properties will be presented and discussed. Furthermore, recent results concerning the relationship between the nano/microstructure of PDC-NCs and their properties will be highlighted.

Robust Ti3C2Tx MXene foam modified with natural antioxidants for long-term effective electromagnetic interference shielding.

MXenes have been proven to be outstanding lossy phase of advanced electromagnetic interference (EMI) shielding materials. However, their poor tolerance to oxygen and water results in fast degradation of the pristine two-dimensional (2D) nanostructure and fading of the functional performance. Herein, in this research, natural antioxidants (e.g., melatonin, tea polyphenols, and phytic acid) were employed to protect the Ti3C2Tx MXene from its degradation in order to achieve a long-term stability of the EMI shielding performance. The results showed that the synthesized composites comprised of antioxidants and Ti3C2Tx exhibited a decelerating degradation rate resulting in an improved EMI shielding effective (SE) stability. The antioxidation mechanism of the applied antioxidants is discussed with respect to the nanostructure evolution of the Ti3C2Tx MXene. This work contributes to the basic foundations for the further development of advanced MXenes for stable applications in the EM field.

SiCO Ceramics as Storage Materials for Alkali Metals/Ions: Insights on Structure Moieties from Solid-State NMR and DFT Calculations.

Polymer-derived silicon oxycarbide ceramics (SiCO) have been considered as potential anode materials for lithium- and sodium-ion batteries. To understand their electrochemical storage behavior, detailed insights into structural sites present in SiCO are required. In this work, the study of local structures in SiCO ceramics containing different amounts of carbon is presented. 13 C and 29 Si solid-state MAS NMR spectroscopy combined with DFT calculations, atomistic modeling, and EPR investigations, suggest significant changes in the local structures of SiCO ceramics even by small changes in the material composition. The provided findings on SiCO structures will contribute to the research field of polymer-derived ceramics, especially to understand electrochemical storage processes of alkali metal/ions such as Na/Na+ inside such networks in the future.

Molybdenum Phosphide Quantum Dots Encapsulated by P/N-Doped Carbon for Hydrogen Evolution Reaction in Acid and Alkaline Electrolytes.

A facile and eco-friendly strategy is presented for synthesizing novel nanocomposites, with MoP quantum dots (QDs) as cores and graphitic carbon as shells, these nanoparticles are dispersed in a nitrogen and phosphorus-doped porous carbon and carbon nanotubes (CNTs) substrates (MoP@NPC/CNT). The synthesis involves self-assembling reactions to form single-source precursors (SSPs), followed by pyrolysis at 900 °C in an inert atmosphere to obtain MoP@NPC/CNT-900. The presence of carbon layers on the MoP QDs effectively prevents particle aggregation, enhancing the utilization of active MoP species. The optimized sample, MoP@NPC/CNT-900, exhibits remarkable electrocatalytic activity and durability for the hydrogen evolution reaction (HER). It demonstrates a low overpotential of 155 mV at 10 mA cm-2 , a small Tafel slope of 76 mV dec-1 , and sustained performance over 20 hours in 0.5 M H2 SO4 . Furthermore, the catalyst shows excellent activity in 1 M KOH, with a relatively low overpotential of 131 mV and long-term durability under constant current input. The exceptional HER activity can be attributed to several factors: the superior performance of MoP QDs, the large surface area and good conductivity of the carbon substrates, and the synergistic effect between MoP and carbon species.

A facile strategy for reclaiming discarded graphite and harnessing the rate capabilities of graphite anodes.

Graphite negative electrodes are unbeaten hitherto in lithium-ion batteries (LiBs) due to their unique chemical and physical properties. Thus, the increasing scarcity of graphite resources makes smart recycling or repurposing of discarded graphite particularly imperative. However, the current recycling techniques still need to be improved upon with urgency. Herein a facile and efficient hydrometallurgical process is reported to effectively regenerate aged (39.5 %, 75 % state-of-health, SOH) scrapped graphite (SG) from end-of-life lithium-ion batteries. Ultimately, the first cycle reversible capacity of SG1 (SOH = 39.5 %) improved from 266 mAh/g to 337 mAh/g while 330 mAh/g (98 %) remain after 100 cycles at 0.5 C. The reversible capacity for the first cycle of SG2 (SOH = 75 %) boosted from 335 mAh/g to 366 mAh/g with the capacity retention of 99.3 % after 100 cycles at 0.5 C, which is comparable with the benchmark commercial graphite. The regenerated graphites RG1 and RG2 exhibit excellent output characteristics even increasing the rate up to 4 C. This is the best rate level reported in the literature to date. Finally, the diffusion coefficient of Li ions during deintercalation and intercalation in the regenerated graphites have been measured by galvanostatic intermittent titration technique (GITT), determining values 2 orders-of-magnitude higher than that of the spent counterparts. Taking advantage of the synergistic effect of acid leaching and heat treatment, this strategy provides a simple and up-scalable method to recycle graphitic anodes.

trans-Bis(acetato-κO)bis-(2-amino-ethanol-κ(2)N,O)nickel(II).

In the title compound, [Ni(CH(3)CO(2))(2)(C(2)H(7)NO)(2)], the Ni(II) cation, located on an inversion center, is N,O-chelated by two 2-amino-ethanol mol-ecules and further coordinated by two monodendate acetate anions in a slightly distorted octa-hedral geometry. The latter is stabilized by intra-molecular O-H⋯O hydrogen bonds involving the non-coordinated O atom of the acetate and the H atom of the hy-droxy group of the 2-amino-ethanol ligand. In the crystal, N-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional supra-molecular framework that involves (a) the coordinated acetate O atom and one of the H atoms of the amino group and (b) the non-coordinated acetate O atom and the other H atom of the amino group.

Electrochemical Performance of Carbon-Rich Silicon Carbonitride Ceramic as Support for Sulfur Cathode in Lithium Sulfur Battery.

As a promising matrix material for anchoring sulfur in the cathode for lithium-sulfur (Li-S) batteries, porous conducting supports have gained much attention. In this work, sulfur-containing C-rich SiCN composites are processed from silicon carbonitride (SiCN) ceramics, synthesized at temperatures from 800 to 1100 °C. To embed sulfur in the porous SiCN matrix, an easy and scalable procedure, denoted as melting-diffusion method, is applied. Accordingly, sulfur is infiltrated under solvothermal conditions at 155 °C into pores of carbon-rich silicon carbonitride (C-rich SiCN). The impact of the initial porosity and microstructure of the SiCN ceramics on the electrochemical performance of the synthesized SiCN-sulfur (SiCN-S) composites is analysed and discussed. A combination of the mesoporous character of SiCN and presence of a disordered free carbon phase makes the electrochemical performance of the SiCN matrix obtained at 900 °C superior to that of SiCN synthesized at lower and higher temperatures. A capacity value of more than 195 mAh/g over 50 cycles at a high sulfur content of 66 wt.% is achieved.

Single-Source-Precursor Derived Transition Metal Alloys Embedded in Nitrogen-Doped Porous Carbons as Efficient Oxygen Evolution Electrocatalysts.

Carbon supported metallic nanomaterials are of great interest due to their low-cost, high durability and promising functional performance. Herein, a highly active oxygen evolution reaction (OER) electrocatalyst comprised of defective carbon shell encapsulated metal (Fe, Co, Ni) nanoparticles and their alloys supported on in-situ formed N-doped graphene/carbon nanotube hybrid is synthesized from novel single-source-precursors (SSP). The precursors are synthesized by a facile one-pot reaction of tannic acid with polyethylenimine and different metal ions and subsequent pyrolysis of the SSP. Benefiting from the heteroatom doping of carbon and formation of well-encapsulated metal/alloy nanoparticles, the obtained FeNi@NC-900 catalyst possesses lowest overpotentials of 310 mV to achieve a current density of 10 mA cm-2 for OER with a small Tafel slope value of 45 mV dec-1 , indicating excellent catalytic performance due to the following features: (1) A synergistic electronic effect among metal alloy nanoparticles, nitrogen-doped carbon, and entangled carbon nanotubes; (2) penetration of electrolyte is promoted towards the active sites through the porous structure of the formed mesoporous carbon clusters; (3) the unique core-shell nanostructure of the hybrid material effectively curbs the degradation of electrocatalyst by protecting the alloy nanoparticles from harsh electrolyte. This work advances an inexpensive and facile method towards the development of transition metal-based hybrid material for potential energy storage and conversion.