An innovative synthesis of carbon-coated TiO2 nanoparticles as a host for Na+ intercalation in sodium-ion batteries.

In this work, an innovative route to synthesize an anatase TiO2@C composite is presented. The synthesis was conducted using a soft chemistry microwave-assisted method using titanium(IV) butoxide as a titanium precursor. The residual (un)converted titanium precursor remaining after TiO2 synthesis was used as a carbon precursor and thermally treated under H2 to obtain nanoparticles of the TiO2@C composite. A superior reversible specific capacity was obtained with TiO2@C (120 mA h g-1 at a C/20 rate, 3rd cycle) compared to that with pristine TiO2 (66.5 mA h g-1 at a C/20 rate, 3rd cycle), in agreement with the importance of carbon coating addition to TiO2 nanoparticles as negative electrode materials for sodium-ion batteries.

FeAu mixing for high-temperature control of light scattering at the nanometer scale.

Control of the optical properties of a nanoparticle (NP) through its structural changes underlies optical data processing, dynamic coloring, and smart sensing at the nanometer scale. Here, we report on the concept of controlling the light scattering by a NP through mixing of weakly miscible chemical elements (Fe and Au), supporting a thermal-induced phase transformation. The transformation corresponds to the transition from a homogeneous metastable solid solution phase of the (Fe,Au) NP towards an equilibrium biphasic Janus-type NP. We demonstrate that the phase transformation is thermally activated by laser heating up to a threshold of 800 °C (for NPs with a size of hundreds of nm), leading to the associated changes in the light scattering and color of the NP. The results thereby pave the way for the implementation of optical sensors triggered by a high temperature at the nanometer scale via NPs based on metal alloys.

Kinetics vs. thermodynamics: walking on the line for a five-fold increase in MnSi Curie temperature.

Green and digital transitions will induce tremendous demand for metals and semiconductors. This raises concerns about the availability of materials in the rather near future. Addressing this challenge requires an unprecedented effort to discover new materials that are more sustainable and also to expand their functionalities beyond conventional material limits. From this point of view, complex systems combining semiconductor and magnetic properties in a single material lay the foundations for future nanoelectronics devices. Through a combination of out-of-stable equilibrium processes, we achieved fine control over the crystallisation of non-stoichiometric MnSix (x = 0.92). The Curie temperature shows non-monotonous evolution with crystallisation. At the earliest and final stages, the Curie temperature is comparable with stoichiometric MnSi (TC = 30 K). At the intermediate stage, while the material is crystalline and remains non-stoichiometric, a remarkable fivefold increase in Curie temperature (TC = 150 K) is observed. This finding highlights the potential for controlling the metastability of materials as a promising and relatively unexplored pathway to enhance material properties, without relying on critical materials such as rare earth elements.

Laser-Assisted Design of MOF-Derivative Platforms from Nano- to Centimeter Scales for Photonic and Catalytic Applications.

Laser conversion of metal-organic frameworks (MOFs) has recently emerged as a fast and low-energy consumptive approach to create scalable MOF derivatives for catalysis, energy, and optics. However, due to the virtually unlimited MOF structures and tunable laser parameters, the results of their interaction are unpredictable and poorly controlled. Here, we experimentally base a general approach to create nano- to centimeter-scale MOF derivatives with the desired nonlinear optical and catalytic properties. Five three- and two-dimensional MOFs, differing in chemical composition, topology, and thermal resistance, have been selected as precursors. Tuning the laser parameters (i.e., pulse duration from fs to ns and repetition rate from kHz to MHz), we switch between ultrafast nonthermal destruction and thermal decomposition of MOFs. We have established that regardless of the chemical composition and MOF topology, the tuning of the laser parameters allows obtaining a series of structurally different derivatives, and the transition from femtosecond to nanosecond laser regimes ensures the scaling of the derivatives from nano- to centimeter scales. Herein, the thermal resistance of MOFs affects the structure and chemical composition of the resulting derivatives. Finally, we outline the "laser parameters versus MOF structure" space, in which one can create the desired and scalable platforms with nonlinear optical properties from photoluminescence to light control and enhanced catalytic activity.

Surface Modification of Brass via Ultrashort Pulsed Direct Laser Interference Patterning and Its Effect on Bacteria-Substrate Interaction.

In recent decades, antibiotic resistance has become a crucial challenge for human health. One potential solution to this problem is the use of antibacterial surfaces, i.e., copper and copper alloys. This study investigates the antibacterial properties of brass that underwent topographic surface functionalization via ultrashort pulsed direct laser interference patterning. Periodic line-like patterns in the scale range of single bacterial cells were created on brass with a 37% zinc content to enhance the contact area for rod-shaped Escherichia coli (E. coli). Although the topography facilitates attachment of bacteria to the surface, reduced killing rates for E. coli are observed. In parallel, a high-resolution methodical approach was employed to explore the impact of laser-induced topographical and chemical modifications on the antibacterial properties. The findings reveal the underlying role of the chemical modification concerning the antimicrobial efficiency of the Cu-based alloy within the superficial layers of a few hundred nanometers. Overall, this study provides valuable insight into the effect of alloy composition on targeted laser processing for antimicrobial Cu-surfaces, which facilitates the thorough development and optimization of the process concerning antimicrobial applications.

Tuning the optical band gap and electrical properties of NiO thin films by nitrogen doping: a joint experimental and theoretical study.

A joint experimental and theoretical study is presented to reveal the influence of nitrogen doping on the optical and electrical properties of NiO thin films. Nitrogen addition can significantly enhance the subgap absorption. The molecular state of nitrogen (N2) has been identified in these doped thin films by electron energy loss spectroscopy.

Insights into Solid-To-Solid Transformation of MOF Amorphous Phases.

Metal-organic frameworks (MOFs) have been recently explored as crystalline solids for conversion into amorphous phases demonstrating non-specific mechanical, catalytic, and optical properties. The real-time control of such structural transformations and their outcomes still remain a challenge. Here, we use in situ high-resolution transmission electron microscopy with 0.01 s time resolution to explore non-thermal (electron induced) amorphization of a MOF single crystal, followed by transformation into an amorphous nanomaterial. By comparing a series of M-BTC (M: Fe3+, Co3+, Co2+, Ni2+, and Cu2+; BTC: 1,3,5-benzentricarboxylic acid), we demonstrate that the topology of a metal cluster of the parent MOFs determines the rate of formation and the chemistry of the resulting phases containing an intact ligand and metal or metal oxide nanoparticles. Confocal Raman and photoluminescence spectroscopies further confirm the integrity of the BTC ligand and coordination bond breaking, while high-resolution imaging with chemical and structural analysis over time allows for tracking the dynamics of solid-to-solid transformations. The revealed relationship between the initial and resulting structures and the stability of the obtained phase and its photoluminescence over time contribute to the design of new amorphous MOF-based optical nanomaterials.

Gallium Phosphide Nanowires in a Free-Standing, Flexible, and Semitransparent Membrane for Large-Scale Infrared-to-Visible Light Conversion.

Engineering of nonlinear optical response in nanostructures is one of the key topics in nanophotonics, as it allows for broad frequency conversion at the nanoscale. Nevertheless, the application of the developed designs is limited by either high cost of their manufacturing or low conversion efficiencies. This paper reports on the efficient second-harmonic generation in a free-standing GaP nanowire array encapsulated in a polymer membrane. Light coupling with optical resonances and field confinement in the nanowires together with high nonlinearity of GaP material yield a strong second-harmonic signal and efficient near-infrared (800-1200 nm) to visible upconversion. The fabricated nanowire-based membranes demonstrate high flexibility and semitransparency for the incident infrared radiation, allowing utilizing them for infrared imaging, which can be easily integrated into different optical schemes without disturbing the visualized beam.

Radiolabeling Strategies of Micron- and Submicron-Sized Core-Shell Carriers for In Vivo Studies.

Core-shell particles made of calcium carbonate and coated with biocompatible polymers using the Layer-by-Layer technique can be considered as a unique drug-delivery platform that enables us to load different therapeutic compounds, exhibits a high biocompatibility, and can integrate several stimuli-responsive mechanisms for drug release. However, before implementation for diagnostic or therapeutic purposes, such core-shell particles require a comprehensive in vivo evaluation in terms of physicochemical and pharmacokinetic properties. Positron emission tomography (PET) is an advanced imaging technique for the evaluation of in vivo biodistribution of drug carriers; nevertheless, an incorporation of positron emitters in these carriers is needed. Here, for the first time, we demonstrate the radiolabeling approaches of calcium carbonate core-shell particles with different sizes (CaCO3 micron-sized core-shell particles (MicCSPs) and CaCO3 submicron-sized core-shell particles (SubCSPs)) to precisely determine their in vivo biodistribution after intravenous administration in rats. For this, several methods of radiolabeling have been developed, where the positron emitter (68Ga) was incorporated into the particle's core (co-precipitation approach) or onto the surface of the shell (either layer coating or adsorption approaches). According to the obtained data, radiochemical bounding and stability of 68Ga strongly depend on the used radiolabeling approach, and the co-precipitation method has shown the best radiochemical stability in human serum (96-98.5% for both types of core-shell particles). Finally, we demonstrate the size-dependent effect of core-shell particles' distribution on the specific organ uptake, using a combination of imaging techniques, PET, and computerized tomography (CT), as well as radiometry of separate organs. Thus, our findings open up new perspectives of CaCO3-radiolabeled core-shell particles for their further implementation into clinical practice.

Perovskite-Gallium Phosphide Platform for Reconfigurable Visible-Light Nanophotonic Chip.

Reduction of the wavelength in on-chip light circuitry is critically important not only for the sake of keeping up with Moore's law for photonics but also for reaching toward the spectral ranges of operation of emerging materials, such as atomically thin semiconductors, vacancy-based single-photon emitters, and quantum dots. This requires efficient and tunable light sources as well as compatible waveguide networks. For the first challenge, halide perovskites are prospective materials that enable cost-efficient fabrication of micro- and nanolasers. On the other hand, III-V semiconductor nanowires are optimal for guiding of visible light as they exhibit a high refractive index as well as excellent shape and crystalline quality beneficial for strong light confinement and long-range waveguiding. Here, we develop an integrated platform for visible light that comprises gallium phosphide (GaP) nanowires directly embedded into compact CsPbBr3-based light sources. In our devices, perovskite microcrystals support stable room-temperature lasing and broadband chemical tuning of the emission wavelength in the range of 530-680 nm, whereas GaP nanowaveguides support efficient outcoupling of light, its subwavelength (<200 nm) confinement, and long-range guiding over distances more than 20 µm. As a highlight of our approach, we demonstrate sequential transfer and conversion of light using an intermediate perovskite nanoparticle in a chain of GaP nanowaveguides.

Maximum noble-metal efficiency in catalytic materials: atomically dispersed surface platinum.

Platinum is the most versatile element in catalysis, but it is rare and its high price limits large-scale applications, for example in fuel-cell technology. Still, conventional catalysts use only a small fraction of the Pt content, that is, those atoms located at the catalyst's surface. To maximize the noble-metal efficiency, the precious metal should be atomically dispersed and exclusively located within the outermost surface layer of the material. Such atomically dispersed Pt surface species can indeed be prepared with exceptionally high stability. Using DFT calculations we identify a specific structural element, a ceria "nanopocket", which binds Pt(2+) so strongly that it withstands sintering and bulk diffusion. On model catalysts we experimentally confirm the theoretically predicted stability, and on real Pt-CeO2 nanocomposites showing high Pt efficiency in fuel-cell catalysis we also identify these anchoring sites.