Engineering 2D spin networks by on-surface encapsulation of azafullerene radicals in nanotemplates.

We present an efficient strategy for on-surface engineering of organic metal-free supramolecular complexes with long-term spin protection. By vacuum deposition of azafullerene (CN) monomers on a pre-deposited template layer of [10]cycloparaphenylene ([10]CPP) nanohoops on Au(111) surface we exploit the molecular shape matching between the CN and [10]CPP for the azafullerene encapsulation with nanohoops in a guest-host complexation geometry. CN⊂[10]CPP supramolecular complexes self-assemble into an extended two-dimensional hexagonal lattice yielding a high density network of stable spin-1/2 radicals.

Effect of Crystalline Phase and Facet Nature on the Adsorption of Phosphate Species onto TiO Nanoparticles.

The current use of TiO nanoparticles raises questions about their impact on our health. Cells interact with these nanoparticles via the phospholipid membrane and, in particular, the phosphate head. This highlights the significance of understanding the interaction between phosphates and nanoparticles possessing distinct crystalline structures, specifically anatase and rutile.

Machine learning-guided exploration and experimental assessment of unreported compositions in the quaternary Ti-Zr-Cu-Pd biocompatible metallic glass system.

Due to their outstanding elastic limit, biocompatible Ti-based bulk metallic glasses (BMGs) are candidate materials to decrease the size of medical implants and therefore reduce their invasiveness. However, the practical use of classical Ti-BMGs in medical applications is in part hindered by their high copper content: more effort is thus required to design low-copper Ti-BMGs. In this work, in line with current rise in AI-driven tools, machine learning (ML) approaches, a neural-network ML model is used to explore the glass-forming ability (GFA) of unreported low-copper compositions within the biocompatible Ti-Zr-Cu-Pd system.

Noncontact Layer Stabilization of Azafullerene Radicals: Route toward High-Spin-Density Surfaces.

We deposit azafullerene CN radicals in a vacuum on the Au(111) surface for layer thicknesses between 0.35 and 2.1 monolayers (ML).

Coupling phytoremediation of Pb-contaminated soil and biomass energy production: A comparative Life Cycle Assessment.

Phytoremediation is an in-situ remediation technology based on the ability of plants to fix pollutants from the soil. In this sense, plants such as Festuca arundinacea are a promising for heavy metal removal in contaminated soils. The present work studies phytoremediation for Pb removal from a contaminated soil located in Spain using F.

Pharmacological Dissection of the Crosstalk between Na and Ca Channels in GH3b6 Cells.

Thanks to the crosstalk between Na and Ca channels, Na and Ca homeostasis interplay in so-called excitable cells enables the generation of action potential in response to electrical stimulation. Here, we investigated the impact of persistent activation of voltage-gated Na (Na) channels by neurotoxins, such as veratridine (VTD), on intracellular Ca concentration ([Ca]) in a model of excitable cells, the rat pituitary GH3b6 cells, in order to identify the molecular actors involved in Na-Ca homeostasis crosstalk. By combining RT-qPCR, immunoblotting, immunocytochemistry, and patch-clamp techniques, we showed that GH3b6 cells predominantly express the Na1.

Exsolution of Ni Nanoparticles from A-Site-Deficient Layered Double Perovskites for Dry Reforming of Methane and as an Anode Material for a Solid Oxide Fuel Cell.

Exsolution is a promising technique to design metal nanoparticles for electrocatalysis and renewable energy. In this work, Ni-doped perovskites, (PrBa)MnNiO with = 0, 0.05, 0.

Further Improving Coulombic Efficiency and Discharge Capacity in LiNiO Material by Activating Sluggish ∼3.5 V Discharge Reaction.

The electrochemical activity of LiNiO at the initial cycle and factors affecting its activity were understood. Even though LiNiO can achieve almost theoretical charge capacity, it cannot deliver the theoretical discharge capacity that would result in low 1st Coulombic efficiency (CE). For different upper cut-off voltages at 4.

Semi-Transparent Organic Photovoltaic Cells with Dielectric/Metal/Dielectric Top Electrode: Influence of the Metal on Their Performances.

In order to grow semi-transparent organic photovoltaic cells (OPVs), multilayer dielectric/metal/dielectric (D/M/D) structures are used as a transparent top electrode in inverted OPVs. Two different electrodes are probed, MoO/Ag/MoO and MoO/Ag/Cu:Ag/ZnS. Both of them exhibit high transmission in visible and small sheet resistance.

Nanostructured TiO and PEDOT Electrodes with Photovoltaic Application.

In this work, nanostructured TiO and poly-3,4-ethylenedioxythiophene (PEDOT) layers were electrochemically prepared over transparent electrodes. Morphological characterization evidenced the presence of nanostructures as planed with 50-nm-wide TiO rod formations followed by 30-nm-wide PEDOT wires. Different characterizations were made to the deposits, establishing their composition and optic properties of the deposits.

Fully Exploited Oxygen Redox Reaction by the Inter-Diffused Cations in Co-Free Li-Rich Materials for High Performance Li-Ion Batteries.

To meet the growing demand for global electrical energy storage, high-energy-density electrode materials are required for Li-ion batteries. To overcome the limit of the theoretical energy density in conventional electrode materials based solely on the transition metal redox reaction, the oxygen redox reaction in electrode materials has become an essential component because it can further increase the energy density by providing additional available electrons. However, the increase in the contribution of the oxygen redox reaction in a material is still limited due to the lack of understanding its controlled parameters.

Vapor-Phase Infiltration inside a Microporous Porphyrinic Metal-Organic Framework for Postsynthesis Modification.

Vapor-phase infiltration (VPI), a technique derived from atomic layer deposition (ALD) and based on sequential self-limiting chemistry, is used to modify the stable microporous porphyrin-based metal-organic framework (MOF) MIL-173(Zr). VPI is an appealing approach to modifying MOFs by inserting reactants with atomic precision. The microporous nature and chemical stability of MIL-173 enable postsynthesis modification by VPI without MOF degradation even with extremely reactive precursors such as trimethylaluminum (TMA) and diethylzinc (DEZ).

Direct observation and catalytic role of mediator atom in 2D materials.

The structural transformations of graphene defects have been extensively researched through aberration-corrected transmission electron microscopy (AC-TEM) and theoretical calculations. For a long time, a core concept in understanding the structural evolution of graphene defects has been the Stone-Thrower-Wales (STW)-type bond rotation. In this study, we show that undercoordinated atoms induce bond formation and breaking, with much lower energy barriers than the STW-type bond rotation.

Enhanced bactericidal activity of brucite through partial copper substitution.

Brucite Mg(OH) belongs to a family of two-dimensional compounds with a CdI-type structure built up from layers of edge-sharing octahedra delineating 2D galleries. In the current study, nanometer-sized platelets of copper substituted Mg(OH) were prepared by co-precipitation at room temperature in mixed alkaline (NaOH/NaCO) medium. Very weak substitution of a few hydroxyl ions by carbonate groups was highlighted at first by infrared spectroscopy and then quantified by thermogravimetric (TG) and mass spectrometric (MS) evolved gas analyses.

Tuning the Chemistry of Organonitrogen Compounds for Promoting All-Organic Anionic Rechargeable Batteries.

The ever-increasing demand for rechargeable batteries induces significant pressure on the worldwide metal supply, depleting resources and increasing costs and environmental concerns. In this context, developing the chemistry of anion-inserting electrode organic materials could promote the fabrication of molecular (metal-free) rechargeable batteries. However, few examples have been reported because little effort has been made to develop such anionic-ion batteries.

A new proton-conducting Bi-carboxylate framework.

A new robust Bi-carboxylate metal-organic framework (MOF) IEF-2 was hydrothermally prepared, acting as a proton carrier (σ∼ 1.1 × 10 S cm). Such proton conductivity is among the highest reported so far for purely 3D carboxylate-based MOFs, being explained by the existence of a 1D hydrogen-bond network, as suggested by structural analysis and theoretical studies.

Facile enhancement of bulk heterojunction solar cells performance by utilizing PbSe nanorods decorated with graphene.

An efficient approach for improving the photoelectrical conversion efficiency (PCE) of the bulk heterojunction (BHJ) solar cells, based on poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C butyric acidmethyl ester (PCBM), by incorporating PbSe nanorods decorated with graphene (G) into their active layer has been reported for the first time. Pristine PbSe and PbSe:G composites (with different amount of graphene) are synthesized via hydrothermal process and the formation mechanism is explained. The systematic investigation indicates that the crystallite size of PbSe:G increases with increasing graphene content.

Strong magnetic exchange and frustrated ferrimagnetic order in a weberite-type inorganic-organic hybrid fluoride.

We combine powder neutron diffraction, magnetometry and Fe Mössbauer spectrometry to determine the nuclear and magnetic structures of a strongly interacting weberite-type inorganic-organic hybrid fluoride, FeF(H taz). In this structure, Fe and Fe cations form magnetically frustrated hexagonal tungsten bronze layers of corner-sharing octahedra. Our powder neutron diffraction data reveal that, unlike its purely inorganic fluoride weberite counterparts which adopt a centrosymmetric Imma structure, the room-temperature nuclear structure of FeF(H taz) is best described by a non-centrosymmetric Ima2 model with refined lattice parameters a = 9.

Enhanced Stability and Band Gap Tuning of α-[HC(NH)]PbI Hybrid Perovskite by Large Cation Integration.

We report room-temperature synthesis of lead- and iodide-deficient α-[HC(NH)]PbI perovskites (abbreviated d-α-FAPI, FA = formamidinium), with the general formula (A',FA)[PbI] (with A' = hydroxyethylammonium (HEA) or thioethylammonium (TEA) cations, 0.04 ≤ x ≤ 0.15).

Fluorescent Zr(IV) Metal-Organic Frameworks Based on an Excited-State Intramolecular Proton Transfer-Type Ligand.

We report here the preparation of a series of Zr(IV) metal-organic frameworks (MOFs) of the MIL-140 structure type incorporating a ligand exhibiting an intense excited-state intramolecular proton transfer (ESIPT) fluorescence. These solids were obtained by systematically varying the substitution rate of 4,4'-biphenyldicarboxylate by 2,2'-bipyridine-3,3'-diol-5,5'-dicarboxylate, and they were thoroughly characterized by complementary techniques, including high-resolution powder X-ray diffraction, solid-state NMR spectroscopy, nitrogen sorption experiments, and time-resolved fluorescence. We show that the incorporation of the ESIPT-type ligand induces an increase of the hydrophilicity, leading ultimately to a higher sensitivity toward hydrolysis, a phenomenon rarely observed in this structure type, which is considered as one of the most stable among the Zr carboxylate MOFs.

Study of Immersion of LiNiMnCoO Material in Water for Aqueous Processing of Positive Electrode for Li-Ion Batteries.

The understanding of the phenomena occurring during immersion of LiNiMnCoO (NMC) in water is helpful to devise new strategies toward the implementation of aqueous processing of this high-capacity cathode material. Immersion of NMC powder in water leads to both structural modification of the particles surface as observed by high-resolution scanning transmission electron microscopy and the formation of lithium-based compounds over the surface (LiOH, LiCO) in greater amount than after long-time exposure to ambient air, as confirmed by pH titration and Li MAS NMR analysis. The surface compounds adversely affect the electrochemical performance and are notably responsible for the alkaline pH of the aqueous slurry, which causes corrosion of the aluminum collector during coating of the electrode.

PANI Branches onto Donor-Acceptor Copolymers: Synthesis, Characterization and Electroluminescent Properties of New 2D-Materials.

A new series of two-dimensional statistical conjugated polymers based on aniline and 9,9-dihexylfluorene as donor units and benzo- or naphtho-quinoxaline/thiadiazole derivatives as acceptor moieties, possessing PANI segments as side chains, were designed and synthesized. To investigate the effects of the perpendicular PANI branches on the properties of the main chain, the optical, electrochemical, morphological and electroluminescence properties were studied. The 2D materials tend to possess lower molecular weights and to absorb and to emit light red-shifted compared to the trunk 1D-polymers, in the yellow-red region of the visible spectrum.

Sub-Micron Spatial Resolution in Far-Field Raman Imaging Using Positivity-Constrained Super-Resolution.

Raman microscopy is a valuable tool for detecting physical and chemical properties of a sample material. When probing nanomaterials or nanocomposites the spatial resolution of Raman microscopy is not always adequate as it is limited by the optical diffraction limit. Numerical post-processing with super-resolution algorithms provides a means to enhance resolution and can be straightforwardly applied.