Deciphering Sodium-Ion Storage: 2D-Sulfide versus Oxide Through Experimental and Computational Analyses.

Transition metal derivatives exhibit high theoretical capacity, making them promising anode materials for sodium-ion batteries. Sulfides, known for their superior electrical conductivity compared to oxides, enhance charge transfer, leading to improved electrochemical performance. Here, a hierarchical WS2 micro-flower is synthesized by thermal sulfurization of WO3. Comprising interconnected thin nanosheets, this structure offers increased surface area, facilitating extensive internal surfaces for electrochemical redox reactions. The WS2 micro-flower demonstrates a specific capacity of ≈334 mAh g-1 at 15 mA g-1, nearly three times higher than its oxide counterpart. Further, it shows very stable performance as a high-temperature (65 °C) anode with ≈180 mAh g-1 reversible capacity at 100 mA g-1 current rate. Post-cycling analysis confirms unchanged morphology, highlighting the structural stability and robustness of WS2. DFT calculations show that the electronic bandgap in both WS2 and WO3 increases when going from the bulk to monolayers. Na adsorption calculations show that Na atoms bind strongly in WO3 with a higher energy diffusion barrier when compared to WS2, corroborating the experimental findings. This study presents a significant insight into electrode material selection for sodium-ion storage applications.

Unlocking the Potential: Atomically Thin 2D Fluoritene from Exfoliated Fluorite Ore and Its Electrochemical Activity.

Fluorite mineral holds significant importance because of its optoelectronic properties and wide range of applications. Here, we report the successful exfoliation of bulk fluorite ore (calcium fluoride, CaF2) crystals into atomically thin two-dimensional fluoritene (2D CaF2) using a highly scalable liquid-phase exfoliation method. The microscopic and spectroscopy characterizations show the formation of (111) plane-oriented 2D CaF2 sheets with exfoliation-induced material strain due to bond breaking, leading to the changes in lattice parameter. Its potential role in electrocatalysis is further explored for deeper insight, and a probable mechanism is also discussed. The 2D CaF2 with long-term stability shows overpotential values of 670 and 770 mV vs RHE for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively, at 10 mA cm-2. Computational simulations demonstrate the unique "direct-indirect" band gap switching with odd and even numbers of layers. Current work offers new avenues for exploring the structural and electrochemical properties of 2D CaF2 and its potential applicability.

Promoting Electrocatalytic Activity and Stability via Er0.4Bi1.6O3-δ In Situ Decorated La0.8Sr0.2MnO3-δ Oxygen Electrode in Reversible Solid Oxide Cell.

Weak electrocatalytic activity of the La0.8Sr0.2MnO3-δ (LSM) oxygen electrode at medium and low temperatures leads to decreasing performance both in the solid oxide fuel cell (SOFC) mode and the solid oxide electrolysis cell (SOEC) mode. Herein, we design an Er0.4Bi1.6O3-δ (ESB) functionalized La0.8Sr0.2MnO3-δ (labeled as LSM/ESB) oxygen electrode via a one-step co-synthesis modified Pechini method. The unique LSM/ESB with polarization resistance of only 0.029 Ω·cm2 at 750 °C enables a highly enhanced rate of oxygen reduction and evolution reaction. The single cell with the LSM/ESB electrode achieves a maximum power density of 1.747 W cm-2 at 750 °C, 2.6 times higher than that of the mechanically mixed LSM-ESB electrode (0.667 W cm-2). In the SOEC mode, it also shows the improved performance of the LSM/ESB electrode. Furthermore, the cell exhibits admirable durability of 90 h in the fuel cell mode and excellent reversibility. The better performance can be concluded as a better surface-active state and a tighter connection between the LSM and ESB particles of LSM/ESB via a co-synthesis process. This work proposes a novel strategy to advance the application of the one-step modified Pechini technology for an efficient and stable oxygen electrode.

Nanoparticle Induced Morphology Modulation in Spin Coated PS/PMMA Blend Thin Films.

The influence of adding nanoparticles on the ascast morphology of spin coated immiscible polystyrene/poly(methyl methacrylate) (PS/PMMA) thin films of different thickness (hE) and composition (RB, volume ratio of PS to PMMA) has been explored in this article. To understand the precise effect of nanoparticle addition, the morphology of PS/PMMA thin blend films spin cast from toluene on a native oxide covered silicon wafer substrate was first investigated. It is seen that in particle free films, the generic morphology of the films remains nearly unaltered with increase in hE, for RB = 3:1 and 1:3. In contrast, strong hE dependent morphology transformation is observed in films with RB = 1:1. Subsequently, thiol-capped gold nanoparticles (AuNP) containing films with different particle concentrations (CNP) were cast from the same solvent along with the polymer mixture. We observe that addition of AuNPs barely alters the generic morphology of the films with RB = 3:1. In contrast, the presence of the particles significantly influences the morphology of the films with RB = 1:1 and 1:3, particularly at higher CNP (≈10.0%). X-ray photoelectron spectroscopy and X-ray reflectivity of some samples reveal that the AuNPs tend to migrate to the free surface through the PS phase, thereby stabilizing this layer partially or fully (depending on CNP) against dewetting over a surface of adsorbed PMMA layer and influencing the ascast morphology as a function of CNP. The work is fundamentally important in understanding largely overlooked implications of nanoparticle addition on the morphology of PS/PMMA blend thin films which forms the fundamental basis for future interesting studies involving dynamics of nanoparticles within the blend thin films.

In Situ Synthesis of Mesoporous TiO2 Nanofibers Surface-Decorated with AuAg Alloy Nanoparticles Anchored by Heterojunction Exhibiting Enhanced Solar Active Photocatalysis.

We designed an electrospinning synthesis protocol to obtain in situ, the mesoporous TiO2 nanofibers, which are surface-decorated with plasmonic AuAg nanoparticles (AuAg-mTNF-H). Such alloy nanoparticles are found to be partially exposed on the surface of the nanofibers. Characterization by HRTEM and EDS confirmed the formation of 1:1 AuAg alloy nanoparticles on the surface of TiO2 nanofibers with heterojunction at the interfaces. On the basis of electron microscopic characterization, we proposed that, during the formation of the nanofibers, the incorporated metal ions with surface capping of negative charges migrated toward the outer surface of the nascent fibers under the influence of high positive voltage required for electrospinning. As a result, after the subsequent thermal treatment, the crystallization of TiO2 nanofibers and the formation of alloy nanoparticles took place, leading to the formation of a deep heterojunction through partial embedment of the nanoparticles. The formation of AuAg alloy also restricted the oxidation of Ag, thus making the nanoparticles highly stable in ambient condition. Accordingly, such unique AuAg-mTNF-H photocatalyst shows strong light absorption property covering the entire range of visible wavelengths with stability. The solar light harvesting property of AuAg-mTNF-H was verified by monitoring solar light induced H2 evolution via water splitting and photodecomposition of MB. In both the cases AuAg-mTNF-H showed excellent H2 evolution and photodecomposition of dye.

Electrospun ZrO2 nanofibers: precursor controlled mesopore ordering and evolution of garland-like nanocrystal arrays.

We observed that the hydrolysis-condensation reaction of precursors makes a significant difference in constructing ordered mesopores in electrospun ZrO2 nanofibers. Transmission-SAXS studies confirm the generation of uniform clusters of size ∼1.44 nm in the ZrOCl2·8H2O (inorganic salt) derived sol due to its relatively slow hydrolysis-condensation process. These initial -Zr-O-Zr- clusters acted as building blocks to form uniform 3D ordered cubic (Pm3[combining macron]m) mesopores in the presence of Pluronic F127 surfactant. In contrast, the commonly used Zr-alkoxide (zirconium n-propoxide) precursor, which is highly hydrolysable even after the use of a controlling agent, generates larger clusters with broad size distributions due to the uncontrolled hydrolysis-condensation of alkoxy groups. Accordingly, in the presence of F127, the alkoxide derived sol yielded disordered mesopores in the resultant fibers. XRD under dynamic heating conditions (up to 900 °C) and the corresponding TEM studies of the ZrOCl2·8H2O derived nanofibers confirmed the retention of mesopores even in the extremely thin nanofibers (diameter ∼15-25 nm) after the amorphous to crystal phase transformation (cubic/tetragonal). An interesting morphological transformation has been observed in the nanofibers at 900 °C where the fibers have been uniformly segmented by distinct single nanocrystals (width ∼15-65 nm) with mesopores. Further heat-treatment at 1100 °C made these segmented nanofibers nonporous, and a garland-like appearance with monoclinic nanocrystal arrays was formed.

In Situ Mg/MgO-Embedded Mesoporous Carbon Derived from Magnesium 1,4-Benzenedicarboxylate Metal Organic Framework as Sustainable Li-S Battery Cathode Support.

Development of advanced carbon cathode support with the ability to accommodate high sulfur (S) content as well as effective confinement of the sulfur species during charge-discharge is of great importance for sustenance of Li-S battery. A facile poly(vinylpyrrolidone)-assisted solvothermal method is reported here to prepare Mg-1,4-benzenedicarboxylate metal organic framework (MOF) from which mesoporous carbon is derived by thermal treatment, where the hexagonal sheetlike morphology of the parent MOF is retained. Existence of abundant pores of size 4 and 9 nm extended in three dimensions with zigzag mazelike channels helps trapping of S in the carbon matrix through capillary effect, resulting in high S loading. When tested as a cathode for lithium-sulfur battery, a reversible specific capacity of 1184 mAh g-1 could be achieved at 0.02 C. As evidenced by X-ray photoelectron spectroscopy, in situ generated Mg in the carbon structure enhances the conductivity, whereas MgO provides support to S immobilization through chemical interactions between Mg and sulfur species for surface polarity compensation, restricting the dissolution of polysulfide into the electrolyte, the main cause for the "shuttle phenomenon" and consequent capacity fading. The developed cathode shows good electrochemical stability with reversible capacities of 602 and 328 mAh g-1 at 0.5 and 1.0 C, respectively, with retentions of 64 and 67% after 200 cycles. The simple MOF-derived strategy adopted here would help design new carbon materials for Li-S cathode support.

Functionalized C@TiO2 hollow spherical architecture for multifunctional applications.

Hierarchical anatase titania (TiO2) with a hollow spherical architecture decorated with functionalized carbon dots (C(F)@THS) was synthesized by a solvothermal decomposition of titanium(IV) isopropoxide (TTIP) in the presence of a solution mixture containing thiourea and citric acid. Interestingly, the concomitant presence of thiourea and citric acid has been found to be essential to obtain such hierarchical hollow architecture because individual constituents produced non-hollow spheres when hydrothermally treated with TTIP. The co-existence of these two constituents also accelerates the growth of hollow spheres. BET surface area study of C(F)@THS revealed the existence of a slit like mesoporosity with a surface area value of 81 m(2) g(-1). Time dependent FESEM and TEM studies confirmed the formation of nanoflake like structures in the intermediate stages followed by the growth of a hollow spherical architecture. We proposed that these nanoflakes get accumulated on the bubble surface to form such hollow spherical morphology. The PL spectral study and Raman shift of the as prepared C(F)@THS confirmed the presence of functionalized graphitic C dots on the surface. A thorough XPS analysis was conducted to explore the nature and relative atomic concentration of the functional groups (-COOH, -CONH2, -NH2). This C(F)@THS sample showed very fast and selective dye (methylene blue and methyl violet) adsorption ability (even from a mixture of two different dye solutions) due to these δ-site containing functional groups on the surface. As C(F)@THS showed only two times reusability for adsorption, the dye adsorbed C(F)@THS was calcined at 450 °C in air to yield organic free anatase TiO2 hollow spheres (THS) with a retention of the original structure. THS was recycled as an efficient and a reusable photocatalyst (k = 9.36 × 10(-2) min(-1)) as well as a photoanode in dye sensitized solar cells (DSSCs) having Jsc value of 19.58 mA cm(-2) with overall efficiency of 6.48%.

Electrochemical energy storage in montmorillonite K10 clay based composite as supercapacitor using ionic liquid electrolyte.

Exploring new electrode materials is the key to realize high performance energy storage devices for effective utilization of renewable energy. Natural clays with layered structure and high surface area are prospective materials for electrical double layer capacitors (EDLC). In this work, a novel hybrid composite based on acid-leached montmorillonite (K10), multi-walled carbon nanotube (MWCNT) and manganese dioxide (MnO2) was prepared and its electrochemical properties were investigated by fabricating two-electrode asymmetric supercapacitor cells against activated carbon (AC) using 1.0M tetraethylammonium tetrafluroborate (Et4NBF4) in acetonitrile (AN) as electrolyte. The asymmetric supercapacitors, capable of operating in a wide potential window of 0.0-2.7V, showed a high energy density of 171Whkg(-1) at a power density of ∼1.98kWkg(-1). Such high EDLC performance could possibly be linked to the acid-base interaction of K10 through its surface hydroxyl groups with the tetraethylammonium cation [(C2H5)4N(+) or TEA(+)] of the ionic liquid electrolyte. Even at a very high power density of 96.4kWkg(-1), the cells could still deliver an energy density of 91.1Whkg(-1) exhibiting an outstanding rate capability. The present study demonstrates for the first time, the excellent potential of clay-based composites for high power energy storage device applications.