Colloidal synthesis of the mixed ionic-electronic conducting NaSbS2 nanocrystals.

Solution-based synthesis of mixed ionic and electronic conductors (MIECs) has enabled the development of novel inorganic materials with implications for a wide range of energy storage applications. However, many technologically relevant MIECs contain toxic elements (Pb) or are prepared by using traditional high-temperature solid-state synthesis. Here, we provide a simple, low-temperature and size-tunable (50-90 nm) colloidal hot injection approach for the synthesis of NaSbS2 based MIECs using widely available and non-toxic precursors. Key synthetic parameters (cationic precursor, reaction temperature, and ligand) are examined to regulate the shape and size of the NaSbS2 nanocrystals (NCs). FTIR studies revealed that ligands with carboxylate functionality are coordinated to the surface of the synthesized NaSbS2 NCs. The synthesized NaSbS2 nanocrystals have electronic and ionic conductivities of 3.31 × 10-10 (e-) and 1.9 × 10-5 (Na+) S cm-1 respectively, which are competitive with the ionic and electrical conductivities of perovskite materials generated by solid-state reactions. This research gives a mechanistic understanding and post-synthetic evaluation of parameters influencing the formation of sodium antimony chalcogenides materials.

Nanoceramics of metastable ε-Fe2O3: effect of sintering on the magnetic properties and sub-terahertz electron resonance.

In this study, we demonstrate the sintering of metastable ε-Fe2O3 nanoparticles into nanoceramics containing 98 wt% of the epsilon iron oxide phase and with a specific density of 60%. At room temperature, the ceramics retain a giant coercivity of 20 kOe and a sub-terahertz absorption at 190 GHz inherent in the initial nanoparticles. The sintering leads to an increase in the frequencies of the natural ferromagnetic resonance at 200-300 K and larger coercivities at temperatures below 150 K. We propose a simple but working explanation of the low-temperature dynamics of the macroscopic magnetic parameters of the ε-Fe2O3 materials via the transition of the smallest nanoparticles into a superparamagnetic state. The results are confirmed by the temperature dependence of the magnetocrystalline anisotropy constant and micromagnetic modeling. In addition, based on the Landau-Lifshitz formalism, we discuss features of the spin dynamics in ε-Fe2O3 and the possibility of using nanoceramics as sub-terahertz spin-pumping media. Our observations will expand the applicability of ε-Fe2O3 materials and promote their integration into telecommunication devices of the next generation.

Precursor-Mediated Colloidal Synthesis of Compositionally Tunable Cu-Sb-M-S (M = Zn, Co, and Ni) Nanocrystals and Their Transport Properties.

The solution-based colloidal synthesis of multinary semiconductor compositions has allowed the design of new inorganic materials impacting a large variety of applications. Yet there are certain compositions that have remained elusive-particularly quaternary structures of transition metal-based (e.g., Co, Zn, Ni, Fe, Mn, and Cr) copper antimony chalcogenides. These are widely sought for tuning the electrical and thermal conductivity as a function of the size, composition, and crystal phase. In this work, a facile hot injection approach for the synthesis of three different tetrahedrite-substituted nanocrystals (NCs) (Cu10Zn2Sb4S13, Cu10Co2Sb4S13, and Cu10Ni1.5Sb4S13) and their growth mechanisms are investigated. We reveal that the interplay between the Zn, Ni, and Co precursors on the basis of thiophilicity is key to obtaining pure phase NCs with controlled size and shape. While all of the synthesized crystal phases display outstanding low thermal conductivity, the Cu10.5Sb4Ni1.5S13 system shows the most enhanced electrical conductivity compared to Cu10Zn2Sb4S13 and Cu10Co2Sb4S13. This study highlights an effective synthesis strategy for the growth of complex quaternary nanocrystals and their high potential for application in thermoelectrics.

Correction: High-coercivity hexaferrite ceramics featuring sub-terahertz ferromagnetic resonance.

Correction for 'High-coercivity hexaferrite ceramics featuring sub-terahertz ferromagnetic resonance' by Evgeny A. Gorbachev et al., Mater. Horiz., 2022, 9, 1264-1272, DOI: https://doi.org/10.1039/D1MH01797G.

Subsuming the Metal Seed to Transform Binary Metal Chalcogenide Nanocrystals into Multinary Compositions.

Direct colloidal synthesis of multinary metal chalcogenide nanocrystals typically develops dynamically from the binary metal chalcogenide nanocrystals with the subsequent incorporation of additional metal cations from solution during the growth process. Metal seeding of binary and multinary chalcogenides is also established, although the seed is solely a catalyst for nanocrystal nucleation and the metal from the seed has never been exploited as active alloying nuclei. Here we form colloidal Cu-Bi-Zn-S nanorods (NRs) from Bi-seeded Cu2-xS heterostructures. The evolution of these homogeneously alloyed NRs is driven by the dissolution of the Bi-rich seed and recrystallization of the Cu-rich stem into a transitional segment, followed by the incorporation of Zn2+ to form the quaternary Cu-Bi-Zn-S composition. The present study also reveals that the variation of Zn concentration in the NRs modulates the aspect ratio and affects the nature of the majority charge carriers. The NRs exhibit promising thermoelectric properties with very low thermal conductivity values of 0.45 and 0.65 W/mK at 775 and 605 K, respectively, for Zn-poor and Zn-rich NRs. This study highlights the potential of metal seed alloying as a direct growth route to achieving homogeneously alloyed NRs compositions that are not possible by conventional direct methods or by postsynthetic transformations.

High-coercivity hexaferrite ceramics featuring sub-terahertz ferromagnetic resonance.

Herein, we demonstrate for the first time compact ferrite ceramics with giant coercivity. The materials are manufactured via sintering single-domain Sr0.67Ca0.33Fe8Al4O19 particles synthesized by a citrate-nitrate auto-combustion method. The obtained ceramics show coercivities up to 22.5 kOe and natural ferromagnetic resonance frequencies (NFMR) in a sub-THz range of 160-282 GHz. At a maximum density of 95%, the sample displays coercivity of 18.5 kOe, which is the highest value among dense ferrite materials reported so far. In addition, we report an unusual blueshift of the NFMR frequency from 160 to 200 GHz, which occurs during material sintering.

Synthesis of Sandwiched Composite Nanomagnets by Epitaxial Growth of Fe3O4 Layers on SrFe10Cr2O19 Nanoplates in High-Boiling Organic Solvent.

Herein, we demonstrate the synthesis of sandwiched composite nanomagnets, which consist of hard magnetic Cr-substituted hexaferrite cores and magnetite outer layers. The hexaferrite plate-like nanoparticles, with average dimensions of 36.3 nm × 5.2 nm, were prepared via a glass crystallization method and were covered by spinel-type iron oxide via thermal decomposition of iron acetylacetonate in a hexadecane solution. The hexaferrite nanoplates act as seeds for the epitaxial growth of the magnetite, which results in uniform continuous outer layers on both sides. The thickness of the layers can be adjusted by controlling the concentration of metal ions. In this way, layers with an average thickness of 3.7 and 4.9 nm were obtained. Due to an atomically smooth interface, the magnetic composites demonstrate the exchange coupling effect, acting as single phases during remagnetization. The developed approach can be applied to any spinel-type material with matching lattice parameters and opens the way to expand the performance of hexaferrite nanomagnets due to a combination of various functional properties.

Titanium Oxide Microspheres with Tunable Size and Phase Composition.

Due to their unique physical and chemical properties, monodisperse titanium oxide microspheres can be used in dye-sensitized solar cells, as cosmetic pigments, and for other applications. However, the synthesis of microspheres with narrow size distribution, desired phase composition, and porosity is still a challenge. In this work, spherical titania particles with controllable size, crystallinity, and pore size were obtained by Ti(OnBu)4 hydrolysis in ethanol. The influence of NaOH addition on the particles' size and morphology was investigated for the first time. Particle diameter can be tailored from 300 nm to 1.5 µm by changing water and NaOH concentrations. Particle size was analyzed by the statistical processing of scanning electron microscopy (SEM) images and differential centrifugal sedimentation (DCS) measurements. Optical properties of the microspheres were studied by diffuse reflectance UV-Vis spectroscopy. Thermal and hydrothermal treatment allowed transforming amorphous phase in as-prepared particles into nanocrystalline anatase and/or rutile. Transmission electron microscopy (TEM) study of the lamellae, cut out from spherical particles using focused ion beam (FIB), revealed that as-synthesized microspheres are non-hollow, homogeneous, and crystallize throughout the whole volume of the particle. The spherical particles possess photoprotective properties; the highest sun protection factor (SPF) was observed for amorphous microspheres.

Eco-Friendly Iron-Humic Nanofertilizers Synthesis for the Prevention of Iron Chlorosis in Soybean (Glycine max) Grown in Calcareous Soil.

Iron deficiency is a frequent problem for many crops, particularly in calcareous soils and iron humates are commonly applied in the Mediterranean basin in spite of their lesser efficiency than iron synthetic chelates. Development and application of new fertilizers using nanotechnology are one of the potentially effective options of enhancing the iron humates, according to the sustainable agriculture. Particle size, pH, and kinetics constrain the iron humate efficiency. Thus, it is relevant to understand the iron humate mechanism in the plant-soil system linking their particle size, characterization and iron distribution in plant and soil using 57Fe as a tracer tool. Three hybrid nanomaterials (F, S, and M) were synthesized as iron-humic nanofertilizers (57Fe-NFs) from leonardite potassium humate and 57Fe used in the form of 57Fe(NO3)3 or 57Fe2(SO4)3. They were characterized using Mössbauer spectroscopy, X-ray diffraction (XRD), extended X-ray absorption fine structure spectroscopy (EXAFS), transmission electron microscopy (TEM) and tested for iron availability in a calcareous soil pot experiment carried out under growth chamber conditions. Three doses (35, 75, and 150 µmol pot-1) of each iron-humic material were applied to soybean iron deficient plants and their iron nutrition contributions were compared to 57FeEDDHA and leonardite potassium humate as control treatments. Ferrihydrite was detected as the main structure of all three 57Fe-NFs and the plants tested with iron-humic compounds exhibited continuous long-term statistically reproducible iron uptake and showed high shoot fresh weight. Moreover, the 57Fe from the humic nanofertilizers remained available in soil and was detected in soybean pods. The Fe-NFs offers a natural, low cost and environmental option to the traditional iron fertilization in calcareous soils.

Gold Decoration and Photoresistive Response to Nitrogen Dioxide of WS2 Nanotubes.

Composites of WS2 nanotubes (NT-WS2 ) and gold nanoparticles (AuNPs) were prepared using aqueous HAuCl4 solutions and subjected to surface analysis. The obtained materials were jointly characterized by X-ray photoelectron (XPS), Raman scattering (RSS), and ultraviolet photoelectron (UPS) spectroscopies. Optical extinction spectroscopy and electron energy loss spectroscopy in the scanning transmission electron microscopy regime (STEM-EELS) were also employed to study plasmon features of the nanocomposite. It was found that AuNPs deposition is accompanied by a partial oxidative dissolution of WS2 , whereas Au-S interfacial species could be responsible for the tight contact of metal nanoparticles and the disulfide. A remarkable sensitivity of n-type resistance of NT-WS2 and Au-NT-WS2 to the adsorption of NO2 gas was also demonstrated at room temperature using periodical illumination by a 530 nm light-emitting diode. Au-NT-WS2 nanocomposites are found to possess a higher photoresponse and enhanced sensitivity in the 0.25-2.0 ppm range of NO2 concentration, as compared to the pristine NT-WS2 . This behaviour is discussed within the physisorption-charge transfer model to explore sensing properties of the nanocomposites.

Ca-Al double-substituted strontium hexaferrites with giant coercivity.

We demonstrate that the simultaneous substitution of calcium and aluminum for strontium and iron in strontium hexaferrite results in a significant increase of coercivity up to a record high of 21.3 kOe. We propose that the effect is originated from a crystal structure distortion causing an increase of the magnetocrystalline anisotropy.

Key Roles of Size and Crystallinity of Nanosized Iron Hydr(oxides) Stabilized by Humic Substances in Iron Bioavailability to Plants.

Availability of Fe in soil to plants is closely related to the presence of humic substances (HS). Still, the systematic data on applicability of iron-based nanomaterials stabilized with HS as a source for plant nutrition are missing. The goal of our study was to establish a connection between properties of iron-based materials stabilized by HS and their bioavailability to plants. We have prepared two samples of leonardite HS-stabilized iron-based materials with substantially different properties using the reported protocols and studied their physical chemical state in relation to iron uptake and other biological effects. We used Mössbauer spectroscopy, XRD, SAXS, and TEM to conclude on iron speciation, size, and crystallinity. One material (Fe-HA) consisted of polynuclear iron(III) (hydr)oxide complexes, so-called ferric polymers, distributed in HS matrix. These complexes are composed of predominantly amorphous small-size components (<5 nm) with inclusions of larger crystalline particles (the mean size of (11 ± 4) nm). The other material was composed of well-crystalline feroxyhyte (δ'-FeOOH) NPs with mean transverse sizes of (35 ± 20) nm stabilized by small amounts of HS. Bioavailability studies were conducted on wheat plants under conditions of iron deficiency. The uptake studies have shown that small and amorphous ferric polymers were readily translocated into the leaves on the level of Fe-EDTA, whereas relatively large and crystalline feroxyhyte NPs were mostly sorbed on the roots. The obtained data are consistent with the size exclusion limits of cell wall pores (5-20 nm). Both samples demonstrated distinct beneficial effects with respect to photosynthetic activity and lipid biosynthesis. The obtained results might be of use for production of iron-based nanomaterials stabilized by HS with the tailored iron availability to plants. They can be applied as the only source for iron nutrition as well as in combination with the other elements, for example, for industrial production of "nanofortified" macrofertilizers (NPK).