Molten Salt-Assisted Synthesis of Titanium Nitride.

Titanium nitride is an exciting plasmonic material, with optical properties similar to gold. However, synthesizing TiN nanocrystals is highly challenging and typically requires solid-state reactions at very high temperatures (800-1000°C). Here, the synthesis of TiN nanocrystals is achieved at temperatures as low as 350°C, in just 1 h. The strategy comprises molten salt, Mg as reductant and Ca3N2 as nitride source. This brings TiN from the realm of solid-state chemistry into the field of solution-based synthesis in regular, borosilicate glassware.

Ball-milling toward nickel(II) diphosphine complexes for direct use in catalysis.

Mechanochemistry turned out to be a powerful synthetic tool enabling the first efficient synthesis of nickel(II) complexes with diphosphine.). It has been demonstrated that solventless ball-milling of nickel(II) halides with diphosphines leads to the [NiX2(diphosphine)] type compounds, which can be directly used in catalysis without any purification. Moreover, it was confirmed that despite the presence of impurities in the resulting complexes, their catalytic activity remains identical to those obtained via traditional solvent-based methods.

High-Pressure Synthesis and Recovery of Single Crystals of the Metastable Manganese Carbide, MnCx.

Transition metal carbides find widespread use throughout industry due to their high strength and resilience under extreme conditions. However, they remain largely limited to compounds formed from the early d-block elements, since the mid-to-late transition metals do not form thermodynamically stable carbides. We report here the high-pressure bulk synthesis of large single crystals of a novel metastable manganese carbide compound, MnCx (P63/mmc), which adopts the anti-NiAs-type structure with significant substoichiometry at the carbon sites. We demonstrate how synthesis pressure modulates the carbon loading, with ~40 % occupancy being achieved at 9.9 GPa.

Unlocking New Avenues: Solid-State Synthesis of Molecularly Imprinted Polymers.

Molecularly imprinted polymers (MIPs) are established artificial molecular recognition platforms with tailored selectivity towards a target molecule, whose synthesis and functionality are highly influenced by the nature of the solvent employed in their synthesis. Steps towards the "greenification" of molecular imprinting technology (MIT) has already been initiated by the elaboration of green MIT principles; developing MIPs in a solvent-free environment may not only offer an eco-friendly alternative, but could also significantly influence the affinity and expected selectivity of the resulting binding sites. In the current study the first solvent-free mechanochemical synthesis of MIPs via liquid-assisted grinding (LAG) is reported. The successful synthesis of the imprinted polymer was functionally demonstrated by measuring its template rebinding capacity and the selectivity of the molecular recognition process in comparison with the ones obtained by the conventional, non-covalent molecular imprinting process in liquid media. The results demonstrated similar binding capacities towards the template molecule and superior chemoselectivity compared to the solution-based MIP synthesis method. The adoption of green chemistry principles with all their inherent advantages in the synthesis of MIPs may not only be able to alleviate the potential environmental and health concerns associated with their analytical (e.g., selective adsorbents) and biomedical (e.g., drug carriers or reservoirs) applications, but might also offer a conceptual change in molecular imprinting technology.

Characterization of Mn5Ge3 Contacts on a Shallow Ge/SiGe Heterostructure.

Mn5Ge3 is a ferromagnetic phase of the Mn-Ge system that is a potential contact material for efficient spin injection and detection. Here, we investigate the creation of Mn5Ge3-based contacts on a Ge/SiGe quantum well heterostructure via solid-state synthesis. X-ray diffraction spectra fitting indicates the formation of Mn5Ge3-based contacts on bulk Ge and Ge/SiGe. High-resolution scanning transmission electron microscopy imaging and energy dispersive X-ray spectroscopy verify the correct Mn5Ge3-based phase formation. Schottky diode measurements, transmission line measurements, and Hall measurements reveal that Mn5Ge3-based contacts serve as good p-type contacts for Ge/SiGe quantum well heterostructures due to having a low Schottky barrier height of 0.10eV (extracted from a Mn5Ge3/n-Ge analogue) and a contact resistance in the order of 1 kΩ. Furthermore, we show that these electrical characteristics have a gate-voltage dependence, thereby providing tunability.

One-pot green solid-state synthesis of Cu2O/microcrystalline cellulose composite with high anti-pathogenic activity.

Cuprous oxide (Cu2O) is proven as an excellent anti-harmful microbial material. However, the liquid and vapor pha5se preparation methods reported so far hardly make pure Cu2O-containing composites and suffer environmental issues caused by chemical reducing agents with multiple processing steps. This work develops a facile one-pot solid-state sintering method to synthesize Cu2O/microcrystalline cellulose (MCC) composite via the thermal decomposition and oxidation-reduction reactions where copper formate was reduced by MCC. The Cu2O/MCC composite exhibits superior purity, dispersibility, stability, high yield, and high efficacy of antibacterial and antiviral properties, e.g., against E. coli, S. aureus, and Equine Arteritis Viral. This work utilizes elegantly the strong reducing capability of cellulose to develop an environmentally benign method to prepare high-purity Cu2O-polymer composites with low cytotoxicity and cost, which can be incorporated readily into other substrate materials to form various forms of anti-harmful microbial materials widely used in public health care products. In addition, the preparation of Cu2O-containing composites based on the reducing capability of cellulose is also expected to be applied to other cellulose-based materials for the loading of Cu2O particles.

Dynamic Luminescence of Lead-Doped Calcium Zinc Germanate Clinopyroxene for Multimode Anticounterfeiting.

Anticounterfeiting plays an essential role in authenticating genuine documents and combating forged products. To further advance the anticounterfeiting technology, there is a strong demand to design new functional materials with unique properties that will be appropriate for making multimode complex security labels. Recently, dynamic security labels have emerged as a new type of advanced anticounterfeiting method as they can hold a much higher security level than the traditional static ones. In this work, we report that calcium zinc germanate (CZGO) clinopyroxenes doped with lead ions have several interesting optical properties, such as dynamic fluorescence, long persistent luminescence, and photochromism. We find that the concentration of lead dopants can significantly impact the reaction kinetics as well as the crystallinity and luminescence properties of CZGO phosphors. By fully utilizing these unique properties, we have successfully fabricated several security labels with multilevel information encoding and dynamic optical performance. The combination of multimode and dynamic luminescence makes these labels extremely challenging to illegally duplicate. With further optimization, this lead-doped CZGO clinopyroxene can be well-integrated into modern anticounterfeiting techniques that will generate highly secure anticounterfeiting labels to combat fake products.

Thermodynamic Guidelines for the Mechanosynthesis or Solid-State Synthesis of MnFe2O4 at Relatively Low Temperatures.

Herein, thermodynamic assessment is proposed to screen suitable precursors for the solid-state synthesis of manganese ferrite, by mechanosynthesis at room temperature or by subsequent calcination at relatively low temperatures, and the main findings are validated by experimental results for the representative precursor mixtures MnO + FeO3, MnO2 + Fe2O3, and MnO2 +2FeCO3. Thermodynamic guidelines are provided for the synthesis of manganese ferrite from (i) oxide and/or metallic precursors; (ii) carbonate + carbonate or carbonate + oxide powder mixtures; (iii) other precursors. It is also shown that synthesis from metallic precursors (Mn + 2Fe) requires a controlled oxygen supply in limited redox conditions, which is hardly achieved by reducing gases H2/H2O or CO/CO2. Oxide mixtures with an overall oxygen balance, such as MnO + Fe2O3, act as self-redox buffers and offer prospects for mechanosynthesis for a sufficient time (>9 h) at room temperature. On the contrary, the fully oxidised oxide mixture MnO2 + Fe2O3 requires partial reduction, which prevents synthesis at room temperature and requires subsequent calcination at temperatures above 1100 °C in air or in nominally inert atmospheres above 750 °C. Oxide + carbonate mixtures, such as MnO2 +2FeCO3, also yield suitable oxygen balance by the decomposition of the carbonate precursor and offer prospects for mechanosynthesis at room temperature, and residual fractions of reactants could be converted by firing at relatively low temperatures (≥650 °C).

Synthesis and crystal structure of Ba2Y0.87(1)Mn1.71(1)Te5.

We report the structural characterization of a new quaternary telluride, Ba2Y0.87(1)Mn1.71(1)Te5, which was synthesized by the direct reaction of the elements inside a vacuum-sealed fused-silica tube. The quaternary phase is the first member of the Ba-M-Mn-Te system (M = Sc and Y). The composition and structure of the phase were elucidated using SEM-EDX (scanning electron microscopy-energy dispersive X-ray spectrometry) and single-crystal X-ray diffraction (SCXRD) studies. The title phase is nonstoichiometric and crystallizes in the monoclinic system (space group C2/m) having the refined unit-cell parameters a = 15.1466 (8), b = 4.5782 (3), c = 10.6060 (7) Šand ß = 116.956 (2)°, with two formula units (Z = 2). The pseudo-two-dimensional crystal structure of Ba2Y0.87(1)Mn1.71(1)Te5 consists of distorted YTe6 octahedra and MnTe4 tetrahedra as the building blocks of the structure. The YTe6 octahedra are arranged to form infinite one-dimensional chains by sharing edges along the [010] direction. These chains are further connected to the MnTe4 tetrahedra along the c axis to create layered two-dimensional polyanionic [Y0.87(1)Mn1.71(1)Te5]4- units. The stuffing of Ba2+ cations in between the layers of [Y0.87(1)Mn1.71(1)Te5]4- anions brings the charge neutrality of the structure. Each Ba atom in the structure sits at the centre of a distorted monocapped trigonal prism-like polyhedron of seven Te atoms.

A Promising Solid-State Synthesis of LiMn1- yFeyPO4 Cathode for Lithium-ion Batteries.

LiMn1-yFeyPO4 (LMFP) is a significant and cost-effective cathode material for Li-ion batteries, with a higher working voltage than LiFePO4 (LFP) and improved safety features compared to layered oxide cathodes. However, its commercial application faces challenges due to a need for a synthesis process to overcome the low Li-ion diffusion kinetics and complex phase transitions. Herein, a solid-state synthesis process using LFP and nano LiMn0.7Fe0.3PO4 (MF73) is proposed. The larger LFP acts as a structural framework fused with nano-MF73, preserving the morphology and high performance of LFP. These results demonstrate that the solid-state reaction occurs quickly, even at a low sintering temperature of 500 °C, and completes at 700 °C. However, contrary to the expectations, the larger LFP particles disappeared and fused into the nano-MF73 particles, revealing that Fe ions diffuse more easily than Mn ions in the olivine framework. This discovery provides valuable insights into understanding ion diffusion in LMFP. Notably, the obtained LMFP can still deliver an initial capacity of 142.3 mAh g-1, and the phase separation during the electrochemical process is significantly suppressed, resulting in good cycling stability (91.1% capacity retention after 300 cycles). These findings offer a promising approach for synthesizing LMFP with improved performance and stability.

Facilitating Near-Infrared Persistent Luminescence in Cr3+ -Doped Gadolinium Gallium Garnets.

Near-infrared persistent luminescence (NIR PersL) materials provide great potential in the fields of night vision, biological imaging, and information encryption. However, among various crystal structures, Cr3+ -doped gallium garnets show inferior PersL property, which turns out to be the bottleneck of their versatile applications. The rational design and facile preparation of high-performance NIR PersL materials are crucial for the emerging applications. In this work, a series of Gd3 Mgx Gex Ga5-2x O12 :Cr3+ (x = 0, 0.25, 0.5, 0.75, 1) is investigated by microwave-assisted solid-state (MASS) approach. Furthermore, by employing chemical composition co-substitution, PersL performance is further improved and the optimum working temperature is adjusted to the lower temperature at 10 °C. Trap level distribution of Gd3 Mg0.5 Ge0.5 Ga4 O12 :Cr3+ phosphor is revealed based on the temperature and fading-time dependent PersL and thermoluminescence property. Further study demonstrates the reduction of the bandgap and the trap distribution forwards at shallow-lying trap energy levels. The synergistic effect, from both energy-band manipulation and trap-level optimization, facilitates NIR PersL in Cr3+ -doped gadolinium gallium garnets. These findings confirm the applicability of MASS-based bandgap and defect level engineering for improving the PersL properties in non/inferior-PersL materials. This burgeoning MASS method may facilitate a wide range of PersL materials for various emerging applications.

Characterization of an Impedance-Type Humidity Sensor Based on Porous SnO2/TiO2 Composite Ceramics Modified with Molybdenum and Zinc.

In this study, we report on the room-temperature characteristics of an impedance-type humidity sensor based on porous tin oxide/titanium oxide (SnO2/TiO2) composite ceramics modified with Mo and Zn. The SnO2/TiO2-based composites synthesized in the solid-state processing technique have been structurally characterized using X-ray diffraction, scanning electron microscopy, energy dispersive, and Raman spectroscopy. Structural analysis indicated the desired porous nature of the synthesized ceramics for sensing applications, with an average crystallite size in the nano range and a density of about 80%. The humidity-sensing properties were evaluated within a wide relative humidity range from 15% to 85% at room temperature, and the results showed that a better humidity response had a sample with Mo. This humidity-sensing material exhibits a linear impedance change of about two orders of magnitude at the optimal operating frequency of 10 kHz. Furthermore, fast response (18 s) and recovery (27 s), relatively small hysteresis (2.8%), repeatability, and good long-term stability were also obtained. Finally, the possible humidity-sensing mechanism was discussed in detail using the results of complex impedance analysis.

Single Step Solid State Synthesis of Carbon Nanoparticles for Instantaneous Detection of Fe (III) in Water Samples.

Though iron is one of the vital micronutrients in biological systems excess of which is associated with various illness. Consumption of contaminated water and crops because of its extensive industrial utility is one of the major sources for excess iron in living beings. Hence, we have designed a sensor based on carbon nanoparticles for the detection of Fe (III) and we have also attempted to estimate Fe (III) in spiked water samples. Carbon nanoparticles (CNP) with quantum yield of 40.2 % was synthesized by solid state synthesis from aromatic molecular precursors unlike conventional synthesis methodology. The particle size, stability and optical properties of CNP were investigated by microscopic and spectroscopic techniques. CNP manifested a naked color change from colorless to yellow in presence of Fe (III) and 72 % of CNP's emission was quenched at 487 nm on excitation at 377 nm by Fe (III). The detection time was less than a second and limit of detection was calculated as 0.248 µM. The mechanistic aspect of detection was investigated and applicability of CNP was examined in spiked water samples.

Solid-State, Hectogram-Scale Preparation of Red Carbon Dots as Phosphor for Energy-Transfer-Induced High-Quality White LEDs with CRI of 97.

In this study, pre-crystallization-controlled, solid-state preparation of red carbon dots (C-dots) from o-phenylenediamine on a hectogram scale with a 94% yield is reported. Highly efficient red phosphor (C-dots@MCC) is obtained by dispersing the C-dots in microcrystalline cellulose, which matched extremely well with the commercial Y3 Al5 O12 :Ce3+ (YAG) phosphor. White light-emitting diodes (WLEDs) fabricated from the two phosphors emitted warm white light with a correlated color temperature of 3845 K, CIE color coordinates of (0.38, 0.37), and an extremely high color rendering index (CRI) of 95, outperforming all the reported YAG-derived WLEDs. Furthermore, the CRI value of the WLED can be further increased to 97 after fine-tuning, which is the highest CRI for WLEDs of any C-dots derived devices reported so far. The superior performance of the WLED is attributed to a delicate energy transfer between YAG and C-dots@MCC. Most importantly, the WLED maintained excellent stabilities under varied currents, working durations, moistures, and temperatures.

Persistent luminescence dosimetry performance of solid state synthesized BaZrO3 phosphors.

This work reports for the first time on the thermoluminescence (TL) and persistent luminescence (PLu) characterization of BaZrO3 synthesized through solid state reaction. X-Ray diffraction confirmed the crystalline structure of the synthesized phosphors. The characteristic glow curves of the synthesized samples exhibit TL maxima located at 85 and 165 °C, whose fading after radiation exposure gives rise to intense PLu. PLu decay curves were recorded after beta particle irradiation in the dose range from 1.0 up to 1024 Gy. Both TL and PLu exhibit remarkable reproducibility. The integrated persistent luminescence (IPLu) as a function of the irradiation dose exhibits a linear dependence in the 1.0-16 Gy dose range, followed by a sublinear behavior from 16 to 128 Gy. From the experimental evidence here presented, it is concluded that solid state synthesized BaZrO3 is an interesting phosphor material to be implemented as a PLu-based detector and dosimeter.

Metal-Enhanced Fluorescent Carbon Quantum Dots via One-Pot Solid State Synthesis for Cell Imaging.

In this study, a facile one-pot solid-state synthesis method is developed to shed light on the metal-enhanced fluorescence (MEF) effect in carbon quantum dots (CQDs) and gold nanoparticles (AuNPs) hybrid materials. This is one of the few studies on the solid-state synthesis of N-doped CQDs/gold hybrid nanomaterials. We have conducted various sets of experiments to reveal the role of individual reagents during the nucleation and growth of nanoparticles. We have demonstrated that the addition of a small amount of gold salt illustrates a paramount effect (103-fold) in photoluminescence intensity. This effect is ascribed to MEF, which is caused due to interactions between the excited-state fluorophores and the free surface electrons of metal nanoparticles. It is interesting to note that a further increase of gold yields fluorescence quenching due to a large number of formed AuNPs causing fluorescence resonance energy transfer. By adjusting the volume ratio of gold salt and CD precursors, it is possible to obtain the CQDs-AuNPs hybrid with the highest fluorescence, which produces extensive visible light under 460 nm excitation. Synthesized materials have been successfully used for imaging human dermal fibroblasts and A549 lung epithelial cells. The dose-dependent cytotoxicity studies reveal that the hybrid structures do not have cytotoxicity.

Sub-10 nm Mixing and Alloying of Cu-Ag and Cu-Ni via Accelerated Solid Diffusion.

Development of nanoscale multicomponent solid inorganic materials is often hindered by slow solid diffusion kinetics and poor precursor mixing in conventional solid-state synthesis. These shortcomings can be alleviated by combining nanosized precursor mixtures and low temperature reaction, which could reduce crystal growth and accelerate the solid diffusion at the same time. However, high throughput production of nanoparticle mixtures with tunable composition via conventional synthesis is very challenging. In this work, we demonstrate that ∼10 nm homogeneous mixing of sub-10 nm nanoparticles can be achieved via spark nanomixing at room temperature and pressure. Kinetically driven Spark Plasma Discharge nanoparticle generation and ambient processing conditions limit particle coarsening and agglomeration, resulting in sub-10 nm primary particles of as-deposited films. The intimate mixing of these nanosized precursor particles enables intraparticle diffusion and formation of Cu/Ni nanoalloy during subsequent low temperature annealing at 100 °C. We also discovered that cross-particle diffusion is promoted during the low-temperature sulfurization of Cu/Ag which tends to phase-segregate, eventually leading to the growth of sulfide nanocrystals and improved homogeneity. High elemental homogeneity, small diffusion path lengths, and high diffusibility synergically contribute to faster diffusion kinetics of sub-10 nm nanoparticle mixtures. The combination of ∼10 nm homogeneous precursors via spark nanomixing, low-temperature annealing, and a wide range of potentially compatible materials makes our approach a good candidate as a general platform toward accelerated solid state synthesis of nanomaterials.

One-Step Solid-State Synthesis of Ni-Rich Cathode Materials for Lithium-Ion Batteries.

Ni-rich cathodes are expected to serve as critical materials for high-energy lithium-ion batteries. Increasing the Ni content can effectively improve the energy density but usually leads to more complex synthesis conditions, thus limiting its development. In this work, a simple one-step solid-state process for synthesizing Ni-rich ternary cathode materials NCA (LiNi0.9Co0.05Al0.05O2) was presented, and the synthesis conditions were systematically studied. It was found that the synthesis conditions have a substantial impact on electrochemical performance. Furthermore, the cathode materials produced through a one-step solid-state process exhibited excellent cycling stability, maintaining 97.2% of their capacity after 100 cycles at a rate of 1 C. The results show that a one-step solid-state method can successfully synthesize Ni-rich ternary cathode material, which has great potential for application. Optimizing the synthesis conditions also provides valuable ideas for the commercial synthesis of Ni-rich cathode materials.

Mechanically Stimulated Solid-State Interaction of Platinum Tetrachloride with Sodium ß-Diketonates.

A new mechanically stimulated solid-state reaction of PtCl4 with sodium ß-diketonates has been discovered. Platinum (II) ß-diketonates were obtained by grinding excess sodium trifluoroacetylacetonate Na(tfac) or hexafluoroacetylacetonate Na(hfac) in a vibration ball mill, followed by subsequent heating of the resulting mixture. The reactions occur under much milder conditions (at about 170 °C) compared to similar reactions of PtCl2 or K2PtCl6 (at about 240 °C). Excess diketonate salt plays the role of a reducing agent in the conversion of Pt (IV) salt to Pt (II) compounds. The effect of grinding on properties of the ground mixtures was studied by XRD, IR, and thermal analysis methods. The difference in the course of the interaction of PtCl4 with Na(hfac) or Na(tfac) indicates the dependence of the reaction on the ligand properties. The probable reaction mechanisms were discussed. This method of synthesis of platinum (II) ß-diketonates makes it possible to substantially reduce the variety of reagents used, the number of reaction steps, the reaction time, the use of solvents, and waste generation compared to conventional solution-based methods.

P2-Type Moisture-Stable and High-Voltage-Tolerable Cathodes for High-Energy and Long-Life Sodium-Ion Batteries.

P2-Na0.67Ni0.33Mn0.67O2 represents a promising cathode for Na-ion batteries, but it suffers from severe structural degradation upon storing in a humid atmosphere and cycling at a high cutoff voltage. Here we propose an in situ construction to achieve simultaneous material synthesis and Mg/Sn cosubstitution of Na0.67Ni0.33Mn0.67O2 via one-pot solid-state sintering. The materials exhibit superior structural reversibility and moisture insensitivity. In-operando XRD reveals an essential correlation between cycling stability and phase reversibility, whereas Mg substitution suppressed the P2-O2 phase transition by forming a new Z phase, and Mg/Sn cosubstitution enhanced the P2-Z transition reversibility benefiting from strong Sn-O bonds. DFT calculations disclosed high chemical tolerance to moisture, as the adsorption energy to H2O was lower than that of the pure Na0.67Ni0.33Mn0.67O2. A representative Na0.67Ni0.23Mg0.1Mn0.65Sn0.02O2 cathode exhibits high reversible capacities of 123 mAh g-1 (10 mA g-1), 110 mAh g-1 (200 mA g-1), and 100 mAh g-1 (500 mA g-1) and a high capacity retention of 80% (500 mA g-1, 500 cycles).