Search Results (1,298)

Manganese- and iron-rich P2-type ${\mathrm{N}\mathrm{a}}_{0.67}{\mathrm{F}\mathrm{e}}_{0.5}{\mathrm{M}\mathrm{n}}_{0.5}{\mathrm{O}}_2 \left(\mathrm{N}\mathrm{F}\mathrm{M}\right)$ has garnered significant interest as a promising cathode candidate due to the natural abundance of Fe and Mn along with a high redox couple of Fe³⁺/Fe⁴⁺ and Mn³⁺/Mn⁴⁺. Despite all these merits, NFM suffers from structural instability during cycling, arising from the destructive Jahn-Teller (JT) distortion effect of Mn³⁺/Mn⁴⁺ during charging and Fe⁴⁺/Fe³⁺ during discharging. In this research, a novel P2-type transition metal-oxide cathode Na_0.67Fe_0.5−2xMn_0.5Ti_xV_xO₂ was synthesized by doping a tiny fraction of two electrochemically inactive elements, Titanium (Ti) and Vanadium (V), into Mn-rich Na_0.67Fe_0.5Mn_0.5O₂ (NFM) that mitigated the JT effect substantially and ameliorated the stability of the SIB during cycling. These exhaustive structural and morphological comparisons provided insights into the effects of V and Ti doping on stabilizing surface structures, reducing Jahn Teller distortion, enhancing stability and capacity retention, and promoting the Na⁺ carrier transport mechanism. Moreover, the electrochemical analysis, such as the galvanostatic charge/discharge profile, validates the capacity improvement via Ti and V co-doping into NFM cathode. The initial discharge capacity of the 2% Ti/V-doped ${\mathrm{N}\mathrm{a}}_{0.67}{\mathrm{F}\mathrm{e}}_{0.48}{\mathrm{M}\mathrm{n}}_{0.5}{{\mathrm{T}\mathrm{i}}_{0.01}{\mathrm{V}}_{0.01}\mathrm{O}}_2 \left(2\mathrm{N}\mathrm{F}\mathrm{M}\mathrm{T}\mathrm{V}\right)$ was found to be 187.12 mAh g⁻¹ at a rate of 0.1 C, which was greater than the discharge capacity of 175.15 mAh g⁻¹ observed for pure NFM ${(\mathrm{N}\mathrm{a}}_{0.67}{\mathrm{M}\mathrm{n}}_{0.5}{\mathrm{F}\mathrm{e}}_{0.5}{\mathrm{O}}_2).$ In contrast, 2NFMTV exhibited a noteworthy capacity retention of 46.1% when evaluated for its original capacity after undergoing 150 cycles at a rate of 0.1 C. This research also established a structural doping approach as a feasible technique for advancing the progress of next-generation Sodium-ion Batteries. Full article

Ceramic proton conductors have the potential to lower the operating temperature of solid oxide cells (SOCs) to the intermediate temperature range of 400–600 °C. This is attributed to their superior ionic conductivity compared to oxide ion conductors under these conditions. However, prominent proton-conducting materials, such as yttrium-doped barium cerates and zirconates with specified compositions like BaCe_1−xY_xO_3−δ (BCY), BaZr_1−xY_xO_3−δ (BZY), and Ba(Ce,Zr)_1−yY_yO_3−δ (BCZY), face significant challenges in achieving dense electrolyte membranes. It is suggested that the incorporation of transition and alkali metal oxides as sintering additives can induce liquid phase sintering (LPS), offering an efficient method to facilitate the densification of these proton-conducting ceramics. However, current research underscores that incorporating these sintering additives may lead to adverse secondary effects on the ionic transport properties of these materials since the concentration and mobility of protonic defects in a perovskite are highly sensitive to symmetry change. Such a drop in ionic conductivity, specifically proton transference, can adversely affect the overall performance of cells. The extent of variation in the proton conductivity of the perovskite BCZY depends on the type and concentration of the sintering aid, the nature of the sintering aid precursors used, the incorporation technique, and the sintering profile. This review provides a synopsis of various potential sintering techniques, explores the influence of diverse sintering additives, and evaluates their effects on the densification, ionic transport, and electrochemical properties of BCZY. We also report the performance of most of these combinations in an actual test environment (fuel cell or electrolysis mode) and comparison with BCZY. Full article

The lanthanide series elements are transition metals used as critical components of electronics, as well as rechargeable batteries, fertilizers, antimicrobials, contrast agents for medical imaging, and diesel fuel additives. With the surge in their utilization, lanthanide metals are being found more in our environment. However, little is known about the health effects associated with lanthanide exposure. Epidemiological studies as well as studies performed in rodents exposed to lanthanum (La) suggest neurological damage, learning and memory impairment, and disruption of neurotransmitter signaling, particularly in serotonin and dopamine pathways. Unfortunately, little is known about the neurological effects of heavier lanthanides. As dysfunctions of serotonergic and dopaminergic signaling are implicated in multiple neurological conditions, including Parkinson’s disease, depression, generalized anxiety disorder, and post-traumatic stress disorder, it is of utmost importance to determine the effects of La and other lanthanides on these neurotransmitter systems. We therefore hypothesized that early-life exposure of light [La (III) or cerium (Ce (III))] or heavy [erbium (Er (III)) or ytterbium (Yb (III))] lanthanides in Caenorhabditis elegans could cause dysregulation of serotonergic and dopaminergic signaling upon adulthood. Serotonergic signaling was assessed by measuring pharyngeal pump rate, crawl-to-swim transition, as well as egg-laying behaviors. Dopaminergic signaling was assessed by measuring locomotor rate and egg-laying and swim-to-crawl transition behaviors. Treatment with La (III), Ce (III), Er (III), or Yb (III) caused deficits in serotonergic or dopaminergic signaling in all assays, suggesting both the heavy and light lanthanides disrupt these neurotransmitter systems. Concomitant with dysregulation of neurotransmission, all four lanthanides increased reactive oxygen species (ROS) generation and decreased glutathione and ATP levels. This suggests increased oxidative stress, which is a known modifier of neurotransmission. Altogether, our data suggest that both heavy and light lanthanide series elements disrupt serotonergic and dopaminergic signaling and may affect the development or pharmacological management of related neurological conditions. Full article

Porphyrin complexes are of great importance due to their possible applications as sensors, solar cells and photocatalysts, as well as their ability to bind additional ligands. A valuable source of knowledge on their nature is their electric properties, which can be evaluated employing density functional theory (DFT) methods, supporting the experimental research. The present work aims at the application of small property-oriented basis sets in calculation of electric properties in transition metals, their oxides and test coordination complexes. Firstly, the existing polarized ZPol basis set for the first-row transition metals is modified in order to improve atomic polarizability results. For this purpose, optimization of the f-type polarization function exponent is carried out with respect to the value of average atomic polarizability of investigated metals. Next, both the original and the modified basis sets are employed in finite field CCSD(T) calculation of transition metal oxides’ dipole moments, as well as DFT calculation of polarizabilities in porphyrin–zinc and porphyrin–zinc–thiazole complexes. The obtained results show that the ZPol and ZPol-A basis sets can be successfully employed in the calculation of linear electric properties in large systems. The optimization procedure used in the present work can be employed for other source basis sets and elements, leading to new efficient polarized basis sets. Full article

For square-planar late transition metal pyridine, diimine (Rh, Ir) complexes with hydro-xido, methoxido, and thiolato ligands. We could previously establish sizable metal-O- and S π-bonding interactions. Herein, we report the hydrogenation studies of iridium hydroxido and methoxido complexes, which quantitatively lead to the trihydride compound and water/methanol. The iridium trihydride displays a highly fluctional structure with scrambling hydrogen atoms, which can be described as a dihydrogen hydride system based on NMR and DFT investigations. This contrasts the iridium sulfur compounds, which are not reacting with dihydrogen. According to DFT and LNO-CCSD(T) calculations, hydrogenation of the methoxido complex proceeds by a two-step mechanism, i.e., an oxidative addition step of H₂ to an Ir(III) dihydride intermediate with consecutive reductive O-H elimination of methanol. Based on PNO-CCSD(T) calculations, the reactivity difference between the O- and S-donors can be traced to the stronger H-O bonds in the water/methanol products compared to the S-H bonds in the sulphur congeners, which serves as a driving force for hydrogenation. Full article

Transition metal oxide magnetite (Fe₃O₄) is recognized as a potential anode material for lithium-ion batteries owing to its high theoretical specific capacity, modest voltage output, and eco-friendly character. It is a challenging task to engineer high-performance composite materials by effectively dispersing Fe₃O₄ crystals with limited sizes in a well-designed supporting framework following sustainable approaches. In this work, the naturally abundant plant products sodium lignosulfonate (Lig) and sodium cellulose (CMC) were selected to coprecipitate with Fe³⁺ ions under mild hydrothermal conditions. The Fe-Lig/CMC intermediate sediment with an optimized microstructure can be directly converted to the Lig/CMC-derived carbon matrix-supported Fe₃O₄ nanocomposite sample (Fe₃O₄@LigC/CC). Compared with the controlled Fe₃O₄@LigC material, the Fe₃O₄@LigC/CC nanocomposite provides superior electrochemical performance in the anode, which has inspiring specific capacities of 820.6 mAh g⁻¹ after 100 cycles under a current rate of 100 mA·g⁻¹ and 750.5 mAh g⁻¹ after 250 cycles, as well as more exciting rate capabilities. The biomimetic sample design and synthesis protocol closely follow the criteria of green chemistry and can be further developed in wider scenarios. Full article

Lithium-titanium-sulfur cathodes have garnered interest due to their distinctive properties and potential applications in lithium-ion batteries. They present various benefits, including lower cost, enhanced safety, and greater energy density compared to the commonly used transition metal oxides. The current trend in lithium-ion batteries is to move to all-solid-state chemistries in order to improve safety and energy density. Several chemistries for solid electrolytes have been studied, tested, and characterized to evaluate the applicability in energy storage system. Among those, sulfur-based Argyrodites have been coupled with cubic rock-salt type Li₂TiS₃ electrodes. In this work, Li₂TiS₃ surfaces were investigated with DFT methods in different conditions, covering the possible configurations that can occur during the cathode usage: pristine, delithiated, and overlithiated. Interfaces were built by coupling selected Li₂TiS₃ surfaces with the most stable Argyrodite surface, as derived from a previous study, allowing us to understand the (electro)chemical compatibility between these two sulfur-based materials. Full article

Silicate glasses containing silicon, sodium, phosphorous, and calcium have the ability to promote bone regeneration and biodegrade as new tissue is generated. Recently, it has been suggested that adding SrO can benefit tissue growth and silicate glass dissolution. Motivated by these recent developments, the effect of SrO/CaO–CaO/SrO substitution on the local structure and dynamics of Si-Na-P-Ca-O oxide glasses has been studied in this work. Differential thermal analysis has been performed to determine the thermal stability of the glasses after the addition of strontium. The local structure has been studied by neutron diffraction augmented by Reverse Monte Carlo simulation, and the local dynamics by neutron Compton scattering and Raman spectroscopy. Differential thermal analysis has shown that SrO-containing glasses have lower glass transition, melting, and crystallisation temperatures. Moreover, the addition of the Sr²⁺ ions decreased the thermal stability of the glass structure. The total neutron diffraction augmented by the RMC simulation revealed that Sr played a similar role as Ca in the glass structure when substituted on a molar basis. The bond length and the coordination number distributions of the network modifiers and network formers did not change when SrO (x = 0.125, 0.25) was substituted for CaO (25-x). However, the network connectivity increased in glass with 12.5 mol% CaO due to the increased length of the Si-O-Si interconnected chain. The analysis of Raman spectra revealed that substituting CaO with SrO in the glass structure dramatically enhances the intensity of the high-frequency band of 1110–2000 cm⁻¹. For all glasses under investigation, the changes in the relative intensities of Raman bands and the distributions of the bond lengths and coordination numbers upon the SrO substitution were correlated with the values of the widths of nuclear momentum distributions of Si, Na, P, Ca, O, and Sr. The widths of nuclear momentum distributions were observed to soften compared to the values observed and simulated in their parent metal-oxide crystals. The widths of nuclear momentum distributions, obtained from fitting the experimental data to neutron Compton spectra, were related to the amount of disorder of effective force constants acting on individual atomic species in the glasses. Full article

Despite considerable progress, high-performing durable catalysts operating under large current densities (i.e., >1000 mA/cm²) are still lacking. To discover platinum group metal-free (PGM-free) electrocatalysts for sustainable energy, our research involves investigating layered topological magnetic materials (semiconducting ferromagnets) as highly efficient electrocatalysts for the hydrogen evolution reaction under high current densities and establishes the novel relations between structure and electrochemical property mechanisms. The materials of interest include transition metal trihalides, i.e., CrCl₃, VCl₃, and VI₃, wherein a structural unit, the layered structure, is formed by Cr (or V) atoms sandwiched between two halides (Cl or I), forming a tri-layer. A few layers of quantum crystals were exfoliated (~50−60 nm), encapsulated with graphene, and electrocatalytic HER tests were conducted in acid (0.5M H₂SO₄) and alkaline (1M KOH) electrolytes. We find a reasonable HER activity evolved requiring overpotentials in a range of 30–50 mV under 10 mA cm⁻² and 400−510 mV (0.5M H₂SO₄) and 280−500 mV (1M KOH) under −1000 mA cm⁻². Likewise, the Tafel slopes range from 27 to 36 mV dec⁻¹ (Volmer–Tafel) and 110 to 190 mV dec⁻¹ (Volmer–Herovsky), implying that these mechanisms work at low and high current densities, respectively. Weak interlayer coupling, spontaneous surface oxidation, the presence of a semi-oxide subsurface (e.g., O–CrCl₃), intrinsic Cl (or I) vacancy defects giving rise to in-gap states, electron redistribution (orbital hybridization) affecting the covalency, and sufficiently conductive support interaction lowering the charge transfer resistance endow the optimized adsorption/desorption strength of H^* on active sites and favorable electrocatalytic properties. Such behavior is expedited for bi-/tri-layers while exemplifying the critical role of quantum nature electrocatalysts with defect sites for industrial-relevant conditions. Full article

Although much information can be gained about thermally induced microstructural changes in metals through the measurement of their thermophysical properties using a differential scanning calorimeter (DSC), due to competing influences on the signal, not all microstructural changes can be fully characterised this way. For example, accurate characterisation of recrystallisation, tempering, and changes in retained delta ferrite in alloyed steels becomes complex due to additional signal changes due to the Curie point, oxidation, and the rate (and therefore the magnitude) of transformation. However, these types of microstructural changes have been shown to invoke strong magnetic and electromagnetic (EM) responses; therefore, simultaneous EM measurements can provide additional complementary data which can help to emphasise or deconvolute these complex signals and develop a more complete understanding of certain metallurgical phenomena. This paper discusses how a DSC machine has been modified to incorporate an EM sensor consisting of two copper coils printed onto either side of a ceramic substrate, with one coil acting as a transmitter and the other as a receiver. The coil is interfaced with a custom-built data acquisition system, which provides current to the transmit coil, records signals from the receive coil, and is controlled by a graphical user interface which allows the user to select multiple excitation frequencies. The equipment has a useable frequency range of approximately 1–100 kHz and outputs phase and magnitude readings at a rate of approximately 50 samples per second. Simultaneous DSC-EM measurements were performed on a nickel sample up to a temperature of 600 °C, with the reversable ferromagnetic to paramagnetic transition in the nickel sample invoking a clear EM response. The results show that the combined DSC-EM apparatus has the potential to provide a powerful tool for the analysis of thermally induced microstructural changes in metals, feeding into research on steel production, development of magnetic and conductive materials, and many more areas. Full article

The development of photoelectrochemical tandem cells for water splitting with electrodes entirely based on metal oxides is hindered by the scarcity of stable p-type oxides and the poor stability of oxides in strongly alkaline and, particularly, strongly acidic electrolytes. As a novelty in the context of transition metal oxide photoelectrochemistry, a bias-free tandem cell driven by simulated sunlight and based on a CuCrO₂ photocathode and a WO₃ photoanode, both unprotected and free of co-catalysts, is demonstrated to split water while working with strongly acidic electrolytes. Importantly, the Faradaic efficiency for H₂ evolution for the CuCrO₂ electrode is found to be about 90%, among the highest for oxide photoelectrodes in the absence of co-catalysts. The tandem cell shows no apparent degradation in short-to-medium-term experiments. The prospects of using a practical cell based on this configuration are discussed, with an emphasis on the importance of modifying the materials for enhancing light absorption. Full article

Gas sensing is essential for detecting and measuring gas concentrations across various environments, with applications in environmental monitoring, industrial safety, and healthcare. The integration of two-dimensional (2D) materials, organic materials, and metal oxides has significantly advanced gas sensor technology, enhancing its sensitivity, selectivity, and response times at room temperature. This review examines the progress in optically activated gas sensors, with emphasis on 2D materials, metal oxides, and organic materials, due to limited studies on their use in optically activated gas sensors, in contrast to other traditional gas-sensing technologies. We detail the unique properties of these materials and their impact on improving the figures of merit (FoMs) of gas sensors. Transition metal dichalcogenides (TMDCs), with their high surface-to-volume ratio and tunable band gap, show exceptional performance in gas detection, especially when activated by UV light. Graphene-based sensors also demonstrate high sensitivity and low detection limits, making them suitable for various applications. Although organic materials and hybrid structures, such as metal–organic frameworks (MoFs) and conducting polymers, face challenges related to stability and sensitivity at room temperature, they hold potential for future advancements. Optically activated gas sensors incorporating metal oxides benefit from photoactive nanomaterials and UV irradiation, further enhancing their performance. This review highlights the potential of the advanced materials in developing the next generation of gas sensors, addressing current research gaps and paving the way for future innovations. Full article

Given the pressing climate and sustainability challenges, shifting industrial processes towards environmentally friendly practices is imperative. Among various strategies, the generation of green, flexible materials combined with efficient reutilization of biomass stands out. This review provides a comprehensive analysis of the hydrothermal carbonization (HTC) process as a sustainable approach for developing carbonaceous materials from biomass. Key parameters influencing hydrochar preparation are examined, along with the mechanisms governing hydrochar formation and pore development. Then, this review explores the application of hydrochars in supercapacitors, offering a novel comparative analysis of the electrochemical performance of various biomass-based electrodes, considering parameters such as capacitance, stability, and textural properties. Biomass-based hydrochars emerge as a promising alternative to traditional carbonaceous materials, with potential for further enhancement through the incorporation of extrinsic nanoparticles like graphene, carbon nanotubes, nanodiamonds and metal oxides. Of particular interest is the relatively unexplored use of transition metal dichalcogenides (TMDCs), with preliminary findings demonstrating highly competitive capacitances of up to 360 F/g when combined with hydrochars. This exceptional electrochemical performance, coupled with unique material properties, positions these biomass-based hydrochars interesting candidates to advance the energy industry towards a greener and more sustainable future. Full article

A series of M(x)CoCeMgAlO mixed oxides with different transition metals (M = Cu, Fe, Mn, and Ni) with an M content x = 3 at. %, and another series of Fe(x)CoCeMgAlO mixed oxides with Fe contents x ranging from 1 to 9 at. % with respect to cations, while keeping constant in both cases 40 at. % Co, 10 at. % Ce and Mg/Al atomic ratio of 3 were prepared via thermal decomposition at 750 °C in air of their corresponding layered double hydroxide (LDH) precursors obtained by coprecipitation. They were tested in a fixed bed reactor for complete methane oxidation with a gas feed of 1 vol.% methane in air to evaluate their catalytic performance. The physico-structural properties of the mixed oxide samples were investigated with several techniques, such as powder X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDX), elemental mappings, inductively coupled plasma optical emission spectroscopy (ICP-OES), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction under hydrogen (H₂-TPR) and nitrogen adsorption–desorption at −196 °C. XRD analysis revealed in all the samples the presence of Co₃O₄ crystallites together with periclase-like and CeO₂ phases, with no separate M-based oxide phase. All the cations were distributed homogeneously, as suggested by EDX measurements and elemental mappings of the samples. The metal contents, determined by EDX and ICP-OES, were in accordance with the theoretical values set for the catalysts’ preparation. The redox properties studied by H₂-TPR, along with the surface composition determined by XPS, provided information to elucidate the catalytic combustion properties of the studied mixed oxide materials. The methane combustion tests showed that all the M-promoted CoCeMgAlO mixed oxides were more active than the M-free counterpart, the highest promoting effect being observed for Fe as the doping transition metal. The Fe(x)CoCeMgAlO mixed oxide sample, with x = 3 at. % Fe displayed the highest catalytic activity for methane combustion with a temperature corresponding to 50% methane conversion, T₅₀, of 489 °C, which is ca. 40 °C lower than that of the unpromoted catalyst. This was attributed to its superior redox properties and lowest activation energy among the studied catalysts, likely due to a Fe–Co–Ce synergistic interaction. In addition, long-term tests of Fe(3)CoCeMgAlO mixed oxide were performed, showing good stability over 60 h on-stream. On the other hand, the addition of water vapors in the feed led to textural and structural changes in the Fe(3)CoCeMgAlO system, affecting its catalytic performance in methane complete oxidation. At the same time, the catalyst showed relatively good recovery of its catalytic activity as soon as the water vapors were removed from the feed. Full article

Transition metal oxides have been widely used in microwave-absorbing materials, but how to improve impedance matching is still an urgent problem. Therefore, we introduced urea as a polymer carbon source into a three-dimensional porous structure modified by Co₃O₄ nanoparticles and explored the influence of different heat treatment temperatures on the wave absorption properties of the composite. The nanomaterials, when calcined at a temperature of 450 °C, exhibited excellent microwave absorption capabilities. Specifically, at an optimized thickness of 9 mm, they achieved a minimum reflection loss (RL_min) of −97.3 dB, accompanied by an effective absorption bandwidth (EAB) of 9.83 GHz that comprehensively covered both the S and Ku frequency bands. On the other hand, with a thickness of 3 mm, the RL_min was recorded as −17.9 dB, with an EAB of 5.53 GHz. This excellent performance is attributed to the multi-facial polarization and multiple reflections induced by the magnetic loss capability of Co₃O₄ nanoparticles, the electrical conductivity of C, and the unique three-dimensional structure of diatomite. For the future development of bio-based microwave absorption, this work provides a methodology and strategy. Full article