Exfoliation of Ca3Co4O9 to Two-Dimensional Single-Crystalline Misfit Calcium Cobaltates for Energy Storage Applications.

Layered materials have become indispensable in the development of two-dimensional (2D) systems, offering extensive specific surface area and exceptional electrical, electrochemical, and optical properties critical for diverse applications in energy storage, catalysis, sensing, and optoelectronics. While mono- and biatomic layered materials have demonstrated remarkable characteristics in lower dimensions, the quest for complexity in materials has opened new avenues for tailoring properties to specific requirements. Within this context, misfit-layered compounds (MLCs) stand out as promising candidates. In this study, we present a successful synthesis of few-layered misfit CaCoO2-CoO2 2D nanosheets in bulk quantities from bulk calcium cobalt oxide (CCO-B or CCO). These newly synthesized 2D exfoliated misfit nanosheets demonstrate remarkable 7-fold electrochemical energy storage properties, surpassing their parent bulk CCO, as cathode materials in aqueous Zn-ion batteries. This work addresses the longstanding challenge of exfoliating bulk MLCs to nanostructured, lower dimensional MLCs, opening doors for utilization in advanced energy storage systems and beyond.

Mechanistic Study of Amphiphilic-Assisted Self-Assembled Cadmium Sulfide Quantum Dots into 3D Superstructures.

Self-assembling of nanoparticles into complex superstructures is very challenging, which usually depends on postorganizing techniques or pre-existing templates such as polypeptide chains or DNA or external stimulus. Such self-assembled processes typically lead to close-packed structures. Here, it has been demonstrated that under carefully template-free reaction conditions CdS quantum dots (QDs) could be synthesized and simultaneously self-assembled into complex superstructures without compromising individual QD properties. The superstructures of CdS QDs attained by the chemical-based method demonstrate Stokes-shifted photoluminescence (PL) from trap states. Remarkably, the PL decay of superstructures exhibits a single-exponential feature. This behavior is unusual for the synthesized superstructures, indicating that the trap states are restricted to a narrow range. The growth mechanism of these superstructures is explained through the formation of liquid crystal phases (LCPs) with the help of a small-angle X-ray scattering (SAXS) analysis.

Two-Dimensional Ultrathin CeVO4 Nanozyme: Fabricated through Non-Oxidic Material.

In recent years, the synthesis of materials in lower dimensions, like two-dimensional (2D) or ultrathin crystals, with distinctive characteristics has attracted substantial scientific attention. The mixed transition metal oxides (MTMOs) nanomaterials are the promising group of materials, which have been extensively utilized for various potential applications. Most of the MTMOs were explored as three-dimensional (3D) nanospheres, nanoparticles, one-dimensional (1D) nanorods, and nanotubes. However, these materials are not well explored in 2D morphology because of the difficulties in removing tightly woven thin oxide layers or exfoliations of 2D oxide layers, which hinder the exfoliation of beneficial features of MTMO. Here, through the exfoliation via Li+ ion intercalation and subsequent oxidation of CeVS3 under hydrothermal condition, we have demonstrated a novel synthetic route for the fabrication of 2D ultrathin CeVO4 NS. The as-synthesized CeVO4 NS exhibit adequate stability and activity in a harsh reaction environment, which gives excellent peroxidase-mimicking activity with a K M value of 0.04 mM, noticeably better than natural peroxidase and previously reported CeVO4 nanoparticles. We have also used this enzyme mimic activity for the efficient detection of biomolecules like glutathione with a LOD of 53 nM.

Spherical Silver Nanocrystals Arranged in a Metastable Square Pattern.

The present article demonstrates the development of two-dimensional (2D) assembly of spherical nanocrystals (NCs) in the square arrangement through the delicate balance between repulsive ligand interactions and attractive van der Waals interactions of NCs, respectively, instead of the otherwise stable hexagonal arrangement. The experimental packing efficiency values matched quite well with the theoretically calculated square arrangement patterns. The above fact indicates that the formation of the 2D square arrangement of silver NCs can be explained by introducing the concept of softness to NCs in the hard sphere model.

Exciton Dynamics in Colloidal CdS Quantum Dots with Intense and Stokes Shifted Photoluminescence in a Single Decay Channel.

CdS quantum dots (QDs), synthesized by a sol-gel method, exhibit significantly Stokes shifted bright photoluminescence (PL), predominantly from the trap states. Surprisingly, the PL decay at the emission maximum is single-exponential. This is an unusual observation for as-prepared QDs and indicates a narrow distribution in the nature of trap states. A closer look reveals an additional fast component for the decays at shorter emission wavelengths, presumably due to the band edge emission, which remains elusive in the steady-state spectra. Indeed, a significantly narrower and blue-shifted emission band is observed in the decay-associated spectra. The contribution of this component to the steady-state PL intensity is shown to be overwhelmed by that of the significantly stronger trap emission. Exciton dynamics in the quantum dots is elucidated using transient absorption spectra, in which the stimulated emission is observed even at low pump power.

Strontium-deficient SrxCoO2-CoO2 nanotubes as a high ampacity and high conductivity material.

Continuous miniaturization of electronics demands the development of interconnectors with high ampacity and high conductivity, which conventional conductors such as copper and gold cannot offer. Here we report the synthesis of Sr-deficient misfit SrxCoO2-CoO2 nanotubes by a novel crystal conversion method and investigate their electrical properties. Bulk Sr6Co5O15 having a quasi-one-dimensional CoO6 polyhedral structure (face-sharing octahedron and trigonal prismatic CoO6 arranged in one-dimension) is converted to SrxCoO2-CoO2 nanotubes where CoO2 adopts a two-dimensional edge-sharing CoO2 layered structure in a basic hydrothermal process. Electrical properties measured on individual nanotubes demonstrate that these nanotubes are semiconducting with a conductivity of 1.28 × 104 S cm-1 and an ampacity of 109 A cm-2, which is the highest reported ampacity value to date of any inorganic oxide-based material. The nanotubes also show a breakdown power per unit channel length (P/L) of ∼38.3 W cm-1, the highest among the regularly used interconnect materials. The above results demonstrate that SrxCoO2-CoO2 nanotubes are potential building blocks for high-power electronic applications.

Cobalt-doped copper vanadate: a dual active electrocatalyst propelling efficient H2 evolution and glycerol oxidation in alkaline water.

Strategically doped metal oxide nanomaterials signify a rapidly growing genre of functional materials with a wide range of practical applications. Copper vanadate (CuV) represents one such highly active system, which has been rarely explored following its doping with an abundant first-row transition metal. Here, we have developed a series of CuV samples with varying cobalt(ii) doping concentrations deploying a relatively simple solid state synthetic procedure. Among the samples, the 10% Co(ii)-doped CuV (Co10%-CuV) exhibited excellent reactivity for both the H2 evolution reaction (HER) and glycerol oxidation reaction (GOR) in an alkaline aqueous medium (pH 14.0) during cathodic and anodic scans, respectively. During this dual-active catalysis, surface-immobilized Co10%-CuV operates at exceptionally low overpotentials of 176 mV and 160 mV for the HER and GOR, respectively, while achieving 10 mA cm2 current density. The detailed spectroscopic analysis revealed the formation of formate as the major product during the GOR with a faradaic efficiency of >90%. Therefore, this Co10%-CuV can be included on either side of a two-electrode electrolyzer assembly to trigger a complete biomass-driven H2 production, establishing an ideal carbon-neutral energy harvest process.

Photoluminescence with Peaked Structure: Inherent to Nanoparticles or Resulting From Impurities in Sample Vial Caps?

We show that fluorescence emission in the visible spectral range reported in the case of many nanoparticles, polymers, complexes and liquid crystals with molecular type signatures could originate from the organic impurities leaching from the caps of glass vials.

Non-Stoichiometry Induced Exsolution of Metal Oxide Nanoparticles via Formation of Wavy Surfaces and their Enhanced Electrocatalytic Activity: Case of Misfit Calcium Cobalt Oxide.

Most heterogeneous catalytic reactions demand high density and yet spatially separated nanoparticles that are strongly anchored on the oxide surfaces. Such nanoparticles can be deposited or synthesized in situ via nonstoichiometric methods. To date, nanoparticles have been exsolved from perovskite oxide surfaces using nonstoichiometric processes. However, the density of the space-separated nanoparticles on the oxide surfaces is still low. And less attention is paid toward the changes that happen to the host during the nanoparticle exsolution process. In this work, we demonstrated in situ exsolution of ultrafine nanoparticles (∼5 nm) of either Co3O4 or Ca(OH)2 via judicious control of nonstoichiometry in a misfit Ca3Co4O9 (CCO). The nanoparticle density over the CCO surface reached as high as 8500/µm2, which is significantly higher than previously reported values. High-resolution electron microscopy studies reveal the formation mechanism of Co3O4 nanoparticles over CCO, and the formation takes palace via the formation of wavy surfaces on the CCO. Defects caused by the nonstoichiometric synthesis created microstrain within the host CCO, resulting in making the new density of states near the Fermi energy. Further, the exsolution process turned the inert host (CCO) into electrocatalytically active toward water splitting. The nonstoichiometric samples obtained by shorter annealing times showed high electrocatalytic behavior for the hydrogen evolution (HER) and oxygen evolution (OER) reactions. The catalytic activity is further enhanced (reaching overpotential of 320 mV and 410 mV for HER and OER respectively, for a current density of 10 mA/cm2) by removing the surface nanoparticles. The observation indicates that the active sites that are produced during the nonstoichiometric synthesis also present in the bulk of the CCO (host). We believe that similar nonstoichiometric synthesis can be applied to a wide variety of tricomponent systems, and they could endow the hosts with novel properties for applications such as catalysis and thermoelectrics.

Microwave-induced electric discharges on metal particles for the synthesis of inorganic nanomaterials under solvent-free conditions.

Microwave irradiation of metals generates electric discharges (arcs). These arcs are used to generate nanoparticles of Cu and Ni and one-dimensional nanorods of CuS, ZnF2, and NiF2 protected with fluorinated amorphous carbon. We have also synthesized reduced graphene oxide and partially rolled graphene by this method.

Voltage Stimulated Anion Binding of Metalloporphyrin-induced Crystalline 2D Nanoflakes.

Voltage-stimulated redox-active materials have received significant attention in the field of organic electronics and sensor technology. Such stimuli-responsive materials trigger the formation of crystalline nanostructures and facilitate the design of efficient smart devices hitherto unknown. Herein, we report that free-base and metallo-tetratolylporphyrin-linked ferrocene derivatives (H2 TTP-Fc and ZnTTP-Fc) undergo distinct proton/anion binding mechanism in CHCl3 during bulk electrolysis at applied voltage of 1.4 V to give [H4 TTP-Fc]+ Cl- and H+ [(Cl)ZnTTP-Fc]- followed by nanospheres and crystalline 2D nanoflakes formation, confirmed by SEM and TEM images, by methanol vapor diffusion (MVD) approach. Moreover, X-ray diffraction analysis suggest that protonated H2 TTP-Fc aggregates exhibit amorphous nature, whereas H+ [(Cl)ZnTTP-Fc]- depict crystalline nature from layer-by-layer arrangement of nanoflakes assisted by π-π stacking and ion-dipole interactions.

Inorganic Nanotubes and Fullerene-like Nanoparticles at the Crossroads between Solid-State Chemistry and Nanotechnology.

Inorganic nanotubes (NTs) and fullerene-like nanoparticles (NPs) of WS2 were discovered some 25 years ago and are produced now on a commercial scale for various applications. This Perspective provides a brief description of recent progress in this scientific discipline. The conceptual evolution leading to the discovery of these NTs and NPs is briefly discussed. Subsequently, recent progress in the synthesis of such NPs from a variety of inorganic compounds with layered (2D) structure is described. In particular, we discuss the synthesis of NTs from chalcogenide- and oxide-based ternary misfit layered compounds, as well as their structure and different growth mechanisms. Next we deliberate on the mechanical, optical, electrical, and electromechanical properties, which delineate them from their bulk counterparts and also from their graphene-like analogues. Here, different experiments with individual NTs coupled with first-principles and molecular dynamics calculations demonstrate the unique physical nature of these quasi-1D nanostructures. Finally, the various applications of the fullerene-like NPs of WS2 and NTs formed therefrom are deliberated. Foremost among the possibilities are their extensive uses as superior solid lubricants. Combined with their nontoxicity and their facile dispersion, these NTs, with an ultimate strength of about 20 GPa, are likely to find numerous applications in reinforcing polymers, adhesives, textiles, medical devices, metallic alloys, and even concrete. Other potential applications in energy-harvesting and catalysis are discussed in brief.

Nanotubes from Oxide-Based Misfit Family: The Case of Calcium Cobalt Oxide.

Misfit layered compounds (MLCs) have generated significant interest in recent years as potential thermoelectric materials. MLC nanotubes could reveal behavior that is entirely different from the bulk material. Recently, new chemical strategies were exploited for the synthesis of nanotubular forms of chalcogenide-based MLCs, which are promising candidates for thermoelectric materials. However, analogous synthesis of oxide-based MLC nanotubes has not been demonstrated until now. Here, we report a chemical strategy for synthesis of cobalt-oxide-based misfit nanotubes. A combination of high-resolution (scanning) transmission electron microscopy (including image simulations), spatially resolved electron energy-loss spectroscopy, electron diffraction, and density functional theory (DFT) calculations is used to discover the formation of a phase within these nanotubes that differs significantly from bulk calcium cobaltite MLCs. Furthermore, DFT calculations show that this phase is semiconducting with a band gap in excess of 1 eV, unlike bulk calcium cobaltite MLCs, which are known to be metallic. Through systematic experiments, we propose a formation mechanism for these nanotubes that could also apply more generally to realizing other oxide-based MLC nanotubes.

Lanthanide-based functional misfit-layered nanotubes.

The synthesis of nanotubes from layered compounds has generated substantial scientific interest. "Misfit" layered compounds (MLCs) of the general formula [(MX)(1+x)](m)[TX2]n, where M can include Pb, Sb, rare earths; T=Cr, Nb, and X=S, Se can form layered structures, even though each sub-system alone is not necessarily a layered or a stable compound. A simple chemical method is used to synthesize these complex nanotubes from lanthanide-based misfit compounds. Quaternary nanotubular structures formed by partial substitution of the lanthanide atom in nanotubes by other elements are also confirmed. The driving force and mechanism of formation of these nanotubes is investigated by systematic temperature and time-dependent studies. A stress-inducement mechanism is proposed to explain the formation of the nanotubes. The resulting materials may find applications in fields that include thermoelectrics, light emitters, and catalysis and address fundamental physical issues in low dimensions.

P-type nitrogen-doped ZnO nanostructures with controlled shape and doping level by facile microwave synthesis.

We report herein the development of a facile microwave irradiation (MWI) method for the synthesis of high-quality N-doped ZnO nanostructures with controlled morphology and doping level. We present two different approaches for the MWI-assisted synthesis of N-doped ZnO nanostructures. In the first approach, N-doping of Zn-poor ZnO prepared using zinc peroxide (ZnO2) as a precursor is carried out under MWI in the presence of urea as a nitrogen source and oleylamine (OAm) as a capping agent for the shape control of the resulting N-doped ZnO nanostructures. Our approach utilizes the MWI process for the decomposition of ZnO2, where the rapid transfer of energy directly to ZnO2 can cause an instantaneous internal temperature rise and, thus, the activation energy for the ZnO2 decomposition is essentially decreased as compared to the decomposition under conductive heating. In the second synthesis method, a one-step synthesis of N-doped ZnO nanostructures is achieved by the rapid decomposition of zinc acetate in a mixture of urea and OAm under MWI. We demonstrate, for the first time, that MWI decomposition of zinc acetate in a mixture of OAm and urea results in the formation of N-doped nanostructures with controlled shape and N-doping level. We report a direct correlation between the intensity of the Raman scattering bands in N-doped ZnO and the concentration of urea used in the synthesis. Electrochemical measurements demonstrate the successful synthesis of stable p-type N-doped ZnO nanostructures using the one-step MWI synthesis and, therefore, allow us to investigate, for the first time, the relationship between the doping level and morphology of the ZnO nanostructures. The results provide strong evidence for the control of the electrical behavior and the nanostructured shapes of ZnO nanoparticles using the facile MWI synthesis method developed in this work.

Nanotubes from Misfit Layered Compounds: A New Family of Materials with Low Dimensionality.

Nanotubes that are formed from layered materials have emerged to be exciting one-dimensional materials in the last two decades due to their remarkable structures and properties. Misfit layered compounds (MLC) can be produced from alternating assemblies of two different molecular slabs with different periodicities with the general formula [(MX)1+x]m[TX2]n (or more simply MS-TS2), where M is Sn, Pb, Bi, Sb, rare earths, T is Sn, Nb, Ta, Ti, V, Cr, and so on, and X is S, Se. The presence of misfit stresses between adjacent layers in MLC provides a driving force for curling of the layers that acts in addition to the elimination of dangling bonds. The combination of these two independent forces leads to the synthesis of misfit layered nanotubes, which are newcomers to the broad field of one-dimensional nanostructures and nanotubes. The synthesis, characterization, and microscopic details of misfit layered nanotubes are discussed, and directions for future research are presented.

Hemocompatibility and macrophage response of pristine and functionalized graphene.

Graphene and its derivatives are being proposed for several important biomedical applications including drug delivery, gene delivery, contrast imaging, and anticancer therapy. Most of these applications demand intravenous injection of graphene and hence evaluation of its hemocompatibility is an essential prerequisite. Herein, both pristine and functionalized graphene are extensively characterized for their interactions with murine macrophage RAW 264.7 cells and human primary blood components. Detailed analyses of the potential uptake by macrophages, effects on its metabolic activity, membrane integrity, induction of reactive oxygen stress, hemolysis, platelet activation, platelet aggregation, coagulation cascade, cytokine induction, immune cell activation, and immune cell suppression are performed using optimized protocols for nanotoxicity evaluation. Electron microscopy, confocal Raman spectral mapping, and confocal fluorescence imaging studies show active interaction of both the graphene systems with macrophage cells, and the reactive oxygen species mediated toxicity effects of hydrophobic pristine samples are significantly reduced by surface functionalization. In the case of hemocompatibility, both types of graphene show excellent compatibility with red blood cells, platelets, and plasma coagulation pathways, and minimal alteration in the cytokine expression by human peripheral blood mononuclear cells. Further, both samples do not cause any premature immune cell activation or suppression up to a relatively high concentration of 75 µg mL(-1) after 72 h of incubation under in vitro conditions. This study clearly suggests that the observed toxicity effects of pristine graphene towards macrophage cells can be easily averted by surface functionalization and both the systems show excellent hemocompatibility.