Synthesis Conditions Research Articles

Uranium Oxide Hydrate Frameworks with Dy(III) or Lu(III) Ions: Insights Into the Framework Structures With Lanthanide Ions.

Two uranium oxide hydrate frameworks (UOHFs) with either Dy3+ or Lu3+ ions, Dy1.36(H2O)6[(UO2)10UO13(OH)4] (UOHF-Dy) or Lu2(H2O)8[(UO2)10UO14(OH)3] (UOHF-Lu), were synthesized hydrothermally and characterized with a range of structural and spectroscopic techniques. Although SEM-EDS analysis confirmed the same atomic ratio of ~5.5 for U : Dy and U : Lu, they displayed different crystal morphologies, needles for UOHF-Dy in the orthorhombic C2221 space group and plates for UOHF-Lu in the triclinic P-1 space group. Both frameworks are composed of β-U3O8 type layers linked by pentagonal bipyramidal uranium polyhedra, with the Dy3+/Lu3+ ions inside the channels. However, the arrangements of Dy3+/Lu3+ ions are different, with disordered Dy3+ ions well aligned at the centers of the channels and single Lu3+ ions well-separated in a zigzag pattern in the channels. While the characteristic vibrational modes were revealed by Raman spectroscopy, the presence of a pentavalent uranium center in UOHF-Lu was confirmed with diffuse reflectance spectroscopy. The formation of two types of UOHFs with lanthanide ions, high or low symmetry, and the structure trend were discussed regards to synthesis conditions and lanthanide ionic radius. This work highlights the complex chemistry driving the formation of UOHFs with lanthanide ions and has implications to the spent nuclear fuel under geological disposal.

Thiol Coordination Softens Liquid Metal Particles To Improve On-Demand Conductivity.

Achieving tunable rupturing of eutectic gallium indium (EGaIn) particles holds great significance in flexible electronic applications, particularly pressure sensors. We tune the mechanosensitivity of EGaIn particles by preparing them in toluene with thiol surfactants and demonstrate an improvement over typical preparations in ethanol. We observe, across multiple length scales, that thiol surfactants and the nonpolar solvent synergistically reduce the applied stress requirements for electromechanical actuation. At the nanoscale, dodecanethiol and propanethiol in toluene suppress gallium oxide growth, as characterized by transmission electron microscopy and X-ray photoelectron spectroscopy. Quantitative AFM imaging produces force-indentation curves and height images, while conductive AFM measures current while probing individual EGaIn particles. As the applied force increases, thiolated particles demonstrate intensified softening, rupturing, and stress-induced electrical activation at forces 40% lower than those for bare particles in ethanol. To confirm that thiolation facilitates rupturing at the macroscale, a laser is used to ablate samples of EGaIn particles. Scanning electron microscopy and resistance measurements across macroscopic samples confirm that thiolated EGaIn particles coalesce to exhibit electrical activation at 0.1 W. Particles prepared in ethanol, however, require 3 times higher laser power to demonstrate a similar behavior. This unique collection of advanced techniques demonstrates that our particle synthesis conditions can facilitate on-demand functionality to benefit electronic applications.

Self-modification of Defective TiO2 under Controlled H2/Ar Gas Environment and Dynamics of Photoinduced Oxygen Vacancies.

In recent years, defective TiO2 has caught considerable research attention because of its potential to overcome the limits of low visible light absorption and fast charge recombination present in pristine TiO2 photocatalysts. Among the different synthesis conditions for defective TiO2, ambient pressure hydrogenation with the addition of Ar as inert gas for safety purposes has been established as an easy to realize process. Whether the Ar gas might still influence the resulting photocatalytic properties and defective surface layer remains an open question. Here, we reveal that the gas flow ratio between H2 and Ar has a crucial impact on the defective structure as well as the photocatalyic activity of TiO2. In particular, transmission electron microscopy (TEM) in combination with electron energy loss spectroscopy (EELS) revealed a larger width of the defective surface layer when using a H2/Ar (50%-50%) gas mixture over pure H2. Here, a possible reason could be the increase in dynamic viscosity of the gas mixture when Ar is added. Additionally, photoinduced enhanced Raman spectroscopy (PIERS) is implemented as a complementary approach to investigate the dynamics of the defective structures under ambient conditions which cannot be effortlessly realized by vacuum techniques like TEM.

On the formation and properties of amorphous and crystalline Li3-yBay/2OCl electrolytes

All-solid-state batteries (ASSBs) have potential to provide higher specific energy, higher power, and longer cycle life than Li-ion batteries (LIBs) for continuously increasing demands of high-performance rechargeable batteries with intrinsic safety. However, one of the barriers for successful design and fabrication of ASSBs is the lack of solid-state electrolytes (SSEs) that can meet multi-functional requirements for ASSBs. To address this issue, the present study investigates hydrothermal synthesis of amorphous and crystalline Ba-doped Li3OCl solid electrolytes and develops the understanding of the relationships between the synthesis conditions and electrochemical properties of the products. It is shown that the formation of an amorphous/crystalline Ba-doped Li3OCl mixture with little hydroxide impurities depends strongly on the hydrothermal reaction temperature, drying temperature, Ba concentration, and rate of removing OH− and H+ ions as steam from water solvated Ba-doped Li3OCl. The key to generate amorphous Li3OCl-based electrolytes with high ionic conductivities (7.65 × 10−3 S/cm) at room temperature is to create non-equilibrium synthesis conditions such as the one identified in this study. The understanding developed in this study will offer critical guidelines for synthesizing amorphous and crystalline Li3OCl-based electrolytes with superior electrochemical properties for ASSBs reliably and reproducibly in the near future.

The Influence of Variations in Synthesis Conditions on the Phase Composition, Strength and Shielding Characteristics of CuBi2O4 Films

The Influence of Variations in Synthesis Conditions on the Phase Composition, Strength and Shielding Characteristics of CuBi2O4 Films

Controlled synthesis of defective MOF-808 and its application in levulinic acid esterification

Defective MOF-808 (Def. MOF-808) plays a pivotal role in catalysis, offering the potential for optimizing catalytic reactions and enhancing reactivity. Through precise control of MOF-808 synthesis conditions, including time, temperature, zirconium (Zr) source, ligand ratio, defect agent type, and content, we systematically studied their effect on material properties. The results showed that by adjusting these conditions, we synthesized a series of MOF-808 materials with varying defect concentrations, referred to as Def. MOF-808. Shorter synthesis times, lower temperatures, defect agents with stronger coordination capabilities, and increased defect agent concentration or reduced organic ligand concentration effectively enhance Def. MOF-808’s defect concentration. The presence of defect sites facilitates the effective binding of the sulfate group, thereby amplifying the level of sulfation and augmenting its acid catalytic potential. Furthermore, this study unveiled a direct link between defect concentration and the catalytic activity observed in the levulinic acid esterification reaction. The Defect-engineered MOF-808 optimized through response surface design demonstrates exceptional heterogeneous acid catalysis performance, achieving impressive conversion rates of 97.5% and selectivity of 96.2%, coupled with remarkable catalytic stability. This study highlights defect engineering as a successful strategy to improve MOF-808 catalyst performance, offering insights for future enhancements.

Activity, stability, and kinetic study of CuO/TiO2 Janus photocatalyst for Rhodamine B degradation

ABSTRACT The CuO/TiO2 photocatalyst was synthesized using hydrothermal and sonochemical methods and subsequently applied to degrade rhodamine B in wastewater. The best synthesis conditions were established, determining Cu(NO3)2 solution concentration of 2.5 wt.% and calcination temperature of 500 °C. The CuO/TiO2 photocatalyst underwent characterization through various techniques, including ICP, photoluminescence, X-ray diffraction, ASAP, scanning electron microscope (SEM), EDAX, transmission electron microscopy (TEM), and diffuse reflectance spectroscopy. TEM and SEM analyses revealed the presence of TiO2 nanowires and CuO nanoparticles. The Box–Behnken design, encompassing 27 experimental runs, assessed the impact of process variables such as initial dye concentration, pH, UV lamp power, and catalyst dose on the degradation process. The model's R2 value of 0.9893 indicated a high precision in fitting the predicted data to their actual values. Analysis of variance results highlighted UV irradiation power as the most significant variable within the design space. In addition, the CuO/TiO2 photocatalyst demonstrated efficacy under visible light irradiation. Light-expanded clay aggregate beads were chosen as the substrate for photocatalyst immobilization, which enhanced the reaction rate. The stability of CuO/TiO2 was evidenced by about 2% reduction in efficiency after four degradation cycles.

Recent and Prospects of Synthesis and Application of Metal-Organic Frameworks (MOFs) in Water Treatment: A Review

AbstractWastewater treatment is designed to eradicate toxic pollutants emanating from the industrial effluent to the surface and underground water. The efficiency and limitations of most of the existing water treatment techniques such as coagulation/flocculation, photocatalysis, membrane technologies and adsorption in the remediation of toxic pollutants have been established. However, the success reported for each of these techniques is usually associated with the efficiency and environmental friendliness of water treatment products applied. MOFs-based products are one of the materials serving as an alternative to chemically synthesized products, and their application as water treatment products has been reported extensively but not systematically documented. In this review, authors endeavoured to comprehensively provide insights into the recent MOFs-based product synthesis for different applications, especially in water treatment. The key factors influencing the synthesis of MOFs, including choice of metal ions, organic linkers, and synthesis conditions, along with the latest developments in scalable and cost-effective fabrication techniques are discussed. The synthesis routes, their limitation and their performances as an adsorbent, photocatalyst and additives in membrane fabrication in the removal of toxic pollutants from water are elaborated. The prospects in the large-scale production of MOFs-based water treatment products for real industrial applications are critically reviewed in this study. Overall, a well-curated synthesis and application of MOFs in water treatment is hereby generated from the best resources accessible through the literature.

Enhancing wearable humidity sensing with conductive PANi-Coated polyurethane nanofibers

This study presents a flexible nanofibrous humidity sensor for wearable applications and smart textiles. The methodology involved fabricating polyurethane (PU) nanofibers via electrospinning, followed by polyaniline (PANi) coating under varied synthesis conditions. Scanning electron microscopy (SEM) analysis revealed consistent diameter uniformity in the prepared PU nanofibers. Moreover, an increase in average nanofiber diameter (305 to 539 nm) was observed with rising polymer solution concentration (7% to 9%). Fourier-transform infrared spectroscopy (FT-IR) confirmed the physical presence of PANi on PU nanofiber surfaces without inducing structural changes. Additionally, the strength of PU nanofibrous samples, with or without PANi coating, increased proportionally with higher PANi and PU polymer concentrations. Electrical conductivity was measured using a four-point device, and surface resistance was assessed across varying humidity levels to study humidity’s impact on samples. Results exhibited a linear relationship between surface electrical resistance and relative humidity changes. Furthermore, the PU and PU/PANi nanofibers exhibit contact angles of 113° and 133°, respectively. The PANi-coated sample is more hydrophobic compared to the uncoated sample. In conclusion, these findings underscore the potential of the developed sensor as a responsive tool for monitoring humidity fluctuations in diverse applications.

In situ cell-scale probing nucleation, growth and evolution of CsPbBr3 nanowires by optical absorption spectroscopy

The growth kinetics of colloidal lead halide perovskite nanomaterials are an integral part of their applications, remains poorly understood due to complex nucleation processes and lack of in situ size monitoring method. Here we demonstrated that absorption spectra can be used to observe in situ growth processes of ultrathin CsPbBr3 nanowires in solution with reference to the effective mass infinite deep square potential well model. By means of this method, we have found that the ultrathin nanowires, fabricated by hot injection method, were firstly formed within one minute. Subsequently, they merge with each other into a thicker structure with increasing reaction time. We revealed that the nucleation, growth, and merging of the CsPbBr3 nanowires are determined by the acid concentration and ligand chain length. At lower acidity, the critical nucleation size of the nanowire is smaller, while the shorter the ligand chain length, the faster the merging among the nanowires. Moreover, the merging mode between nanowires changed with their nucleation size. This growth kinetics of CsPbBr3 nanowires provides a reference for optimizing the synthesis conditions to obtain the one-dimensional CsPbBr3 with desired size, thus enabling accurate control of the nanowire shape.

Microwave‐Assisted Preparation of an Acidic Deep Eutectic Solvent: Green Analysis, Characterization and Application

AbstractMicrowave irradiation was postulated to reduce time and energy for deep eutectic solvent (DES) production which is in line with the principle of green chemistry. In this study, the choline chloride (ChCl)‐malic acid (MA) DES was prepared using microwave‐assisted (DES‐Mic) and conventional (DES‐Con) approaches. Microwave was a relatively greener approach as it was rapid (5 min) and consumed 92.8 % energy less than DES‐Con. Moreover, DES‐Mic and DES‐Con exhibited similar physicochemical profiles (pH, solubility, density) and rheological properties. Structural profiling through FTIR analysis suggested hydrogen bond formation between the functional groups of ChCl and MA. The FTIR spectra also did not show structural differences in the DES synthesized using different methods. DES‐Mic and DES‐Con exhibited superior 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) (80.8±0.1 and 83.2±0.3 %, respectively) free radical scavenging activities than ChCl (15.6±0.8 %), MA (20.0±1.4 %) and ChCl:MA aqueous mixture without subjected to DES synthesis conditions (ChCl:MAaq; 23.3±0.8 %). Both DES were also proven as more efficient solvents for the extraction of polysaccharides from ramie leaf, as they recorded higher yields (21.4±1.9 and 22.2±1.0 %, respectively) than equimolar of MA (17.7±2.6 %) and ChCl (6.4±0.2 %). Overall, microwave was proven as a more sustainable approach for DES preparation compared to conventional method, which could be further improvised for industrial applications.

Optimizing Green Synthesis of Hydrotalcite - Silver Nanoparticles using Syzygium Nervosum based Reducing Agent.

This work aimed to assess the effect of Syzygium nervosum leaf extract as a reducing agent for green synthesis of AgNPs on HT through an optimizing process using response surface methodology (RSM) and the Box-Benken model. The optimal conditions for synthesis of AgNPs on HT include reaction time of 6.15 hours, reaction temperature of 50 oC and the ratio of diluted Syzygium nervosum leaf extract to reduce AgNO3 of 50.37 mL/mg. Under the optimal conditions, the yield of reduction reaction reached 77.54 %, close to the theoretical value of 76.97 %.Besides, the morphology, density, and characteristics of AgNPs on the surface of HT layers have been determined by using Ultraviolet-visible spectroscopy, Field emission scanning electron microscopy, High resolution transmission electron microscopy, selected area diffraction, X-ray diffraction, Dynamic light scattering, Infraredspectroscopy, Fluorescence emission spectroscopy, Brunauer-Emmett-Teller methods. The spherical AgNPs were synthesized successfully on the surface of HT with the average particle size of 13.0 ± 1.1 nm. Interestingly, HT-Ag hybrid materials can inhibit strongly the growth of E. coli, S. aureus as well as two antibiotic resistance bacterial strains, P. stutzeri B27 and antibiotic resistance E. coli. Overall, the HT-Ag hybrid materials are very promising for application in practice.

Optimal conditions for nano-emulsified vegetable oil synthesis for the biostimulation of 1,1,2-trichloroethane and vinyl chloride contaminated groundwater in bioreactors

Contamination of groundwater with chlorinated aliphatic hydrocarbons (CAHs) has become increasingly widespread. Enhanced reductive dechlorination (ERD) by emulsified vegetable oil (EVO) is an environmentally friendly, low-carbon and sustainable technology that effectively eliminates the threat from CAHs. To improve the permeability and bioavailability of EVO in the low-permeability substratum, nano-emulsified vegetable oil (nanoEVO) can be synthesized using a modified phase inversion composition method (MPIC) by increasing the emulsification temperature that reduces the shear force required for the formation of nanodroplets and the interfacial tension between the mixed phase and water. The emulsification temperature of 60 °C, the water content of 40–70%, the droplet diameter (DD) of nanoEVO prepared by MPIC is ∼200 nm, and had good monodispersion (≤0.2). The high molecular weight and low solubility of vegetable oil, and similar size of droplet make nanoEVO remains homogeneous after storage for > one year. NanoEVO can effectively biostimulate indigenous bacteria in CAHs-contaminated groundwater to dechlorinate 1,1,2-trichloroethane (1,1,2-TCA) to ethene via vinyl chloride (VC). The maximum dihaloelimination rate of 1,1,2-TCA was ∼66.06 μM·Cl−·day−1 and the maximum hydrogenolysis rate of VC was ∼35.67 μM·Cl−·day−1. NanoEVO effectively increased the relative abundance of Dehalococcoides from <0.10 to 9.61%. The abundances of Dhc 16S rRNA gene and dehalogenase gene vcrA increased by 102 and 103, respectively. Biostimulation shaped the structure of microbial communities and promoted hydrolytic acidification and anaerobic fermentation. Moreover, the syntrophic VFA-oxidizing bacteria participated in secondary fermentation and were closely correlated with H2 consumption metabolism. By providing carbon sources and maintaining an anaerobic environment with stable pH and ORP, nanoEVO biostimulated the hydrolytic acidification led by fermentative bacteria, secondary fermentation with syntrophic VFA-oxidizing bacteria and reductive dechlorination carried out by dechlorinator, thus greatly increasing the CAH-dechlorinating ability of indigenous microbial communities.

Synthesis of novel Stachytarpheta jamaicensis flower liked hexagonal boron nitride nanoribbons (SJF-BNNBs) to efficiently improve the thermal/mechanical/electrical properties of flexible polyimide films

Heat dissipation has become a bottleneck restricting large-scale integration and flexible electronic technologies. This study reports a novel fabrication strategy to prepare flexible stachytarpheta jamaicensis flower-like hexagonal boron nitride nanoribbons (SJF-BNNBs) and their composite films with polyimide (PI). The effect of synthesis conditions on the morphology of SJF-BNNBs was investigated, and the growth mechanism was proposed. The in-plane and through plane thermal conductivities of the 4 wt% SJF-BNNBs/PI composite film reach 5.98 W m−1 K−1 and 0.79 W m−1 K−1, which are 3047 % and 316 % higher than those of the pure PI film, respectively. The in-plane and through plane thermal conduction enhancement efficiencies reach 761.8 % and 78.9 %, respectively. The tensile strength of the composite film is 61.7 % higher than that of pure PI, and maintains excellent electrical insulating and thermal stability properties. Infrared imaging tests verified the excellent heat dissipation performance of the composite film as a thermal interface material and a flexible copper clad laminate substrate, where the operating temperature of device could be reduced by 17.3 °C. To the best of our knowledge, SJF-BNNBs outperform the most efficient thermally conductive electrically insulating filler and are to break the overcome of polymer composites in heat dissipation applications.

Multimodal responsive Dy3+, Li+ activated Gd2MgTiO6 phosphors for ideal wLED, potent anti-counterfeiting, fingerprint visualization, and encryption coding

The Gd2MgTiO6 is an infant luminescence host that portrays eclectic applications in displays, security devices, and forensic studies. The perovskites are synthesized by facile combustion method, decreasing the synthesis conditions from 1573 K, 5 h to 1173 K, 4 h, from conventional routes. The phosphors are then activated with Dy3+ ions, giving photoluminescence emission in the blue, yellow, and red regions of the visible spectrum owing to (4F9/2 → 6H15/2), (4F9/2 → 6H13/2), and (4F9/2 → 6H11/2) transitions respectively. Further, monovalent Li+, divalent Sr2+, or trivalent Sm3+ ions are co-doped in the crystal matrix, which chiefly enhances the optical and crystalline properties for Li+ sensitization. Under 351 nm excitation, these samples show CIE coordinates (0.3290, 0.3313), color temperature 5759 K, color rendering index 86, and color purity of 2.5 %; signifying ideal white light emission for wLED with quantum efficiency 43 %. Under 980 nm excitation, these phosphors gave noble red emission, which can be effectually applied as a level 3 latent fingerprint visualization tool in criminology. The white and red emissions on UV and NIR excitation respectively are combined for potent anti-counterfeiting security ink and encryption coding; which marked a new methodology for the multifunctional application of a single phosphor matrix.

A General and Highly Versatile Heterogeneous Pd-Catalyzed Oxidative Aminocarbonylation of Alkynes with Aromatic and Aliphatic Amines.

An efficient heterogeneous catalytic system for the oxidative aminocarbonylation of alkynes and amines in the presence of CO/O2 to afford substituted propiolamides has been developed. The active nanocatalyst, [Pd/Mg3Al-LDH]-300(D), is composed by Pd nanoaggregates (2-3 nm average particle size) stabilized over a partially dehydrated [Mg3Al-LDH] matrix. The methodology has resulted widely applicable, being the first catalytic system, either homogeneous or heterogeneous, able to activate not only aliphatic amines but also poorly-nucleophilic aromatic amines. In fact, >60 substituted propiolamides have been synthesized in good to excellent isolated yields through this methodology, being 27 novel compounds. An important characterization effort (XRD, 27Al MAS NMR, TGA, TPD-CO2, BET area, XPS, HAADF-HRSTEM and HRTEM) and optimization of the synthesis conditions of the optimal catalyst has been performed. This study, together with a series of kinetic and mechanistic essays, indicates that the optimal catalyst is composed by Pd(0) species stabilized in a partially dehydrated/dehydroxylated LDH material with a Mg/Al molar ratio of 3 and a small crystallite size. All the experimental data indicates that the in situ formation of [PdI2] active species in the material surface together with the presence of a matrix with the optimal acid/base properties are key aspects of this process.

Hydrothermally Synthesized ZnCr- and NiCr-Layered Double Hydroxides as Hydrogen Evolution Photocatalysts.

The layered double hydroxides (LDHs) of transition metals are of great interest as building blocks for the creation of composite photocatalytic materials for hydrogen production, environmental remediation and other applications. However, the synthesis of most LDHs is reported only by the conventional coprecipitation method, which makes it difficult to control the catalyst's crystallinity. In the present study, ZnCr- and NiCr-LDHs have been successfully prepared using a facile hydrothermal approach. Varying the hydrothermal synthesis conditions allowed us to obtain target products with a controllable crystallite size in the range of 2-26 nm and a specific surface area of 45-83 m2∙g-1. The LDHs synthesized were investigated as photocatalysts of hydrogen generation from aqueous methanol. It was revealed that the photocatalytic activity of ZnCr-LDH samples grows monotonically with the increase in their average crystallite size, while that of NiCr-LDH ones reaches a maximum with intermediate-sized crystallites and then decreases due to the specific surface area reduction. The concentration dependence of the hydrogen evolution activity is generally consistent with the standard Langmuir-Hinshelwood model for heterogeneous catalysis. At a methanol content of 50 mol. %, the rate of hydrogen generation over ZnCr- and NiCr-LDHs reaches 88 and 41 μmol∙h-1∙g-1, respectively. The hydrothermally synthesized LDHs with enhanced crystallinity may be of interest for further fabrication of their nanosheets being promising components of new composite photocatalysts.

Preparation of cationic waterborne polyurethane and its application in leather dyeing

The development of organic chromium-free tanning agents is currently a major research focus in leather tanning. However, these agents decrease the electrical potential of the tanned leather, which hampers the absorption of subsequent anionic dyes and fatliquoring agents. Consequently, issues such as lower color fastness, poor dyeing effects and environmental pollution arise. To address these challenges, this study proposes the utilization of anionic polyurethane (CWPU) as a dye fixing agent to enhance its performance and application in the leather preparation process. CWPU was successfully synthesized using polycarbonate diol (PCDL), isophorone diisocyanate (IPDI), polypropylene glycol (PPG), and N-methyldiethanolamine (MDEA) as raw materials, and the optimal synthesis conditions were optimized. The experimental results showed that the synthesized CWPU color fixing agent exhibited excellent emulsion properties and comprehensive performance when the PCDL: PPG ratio was 1:1 and the MDEA addition amount was 6 wt%. When applied to leather color fixation, the leather not only achieved improved dry and wet rubbing fastness levels of 4–5 but also demonstrated significant improvements in solvent wash resistance and perspiration fastness. Furthermore, the leather treated with CWPU color fixing agent exhibited deeper color and improved physical and mechanical properties and tactile quality. Therefore, this study provides an effective choice of color fixing agent for environmentally friendly chromium-free tanning systems and has broad prospects for the application of acid dyes.

Identification of Degree of Ordering in Spinel LiNi0.5Mn1.5O4 through NMR and Raman Spectroscopies supported by Theoretical Calculations

The performance of the high voltage spinel LiNi0.5Mn1.5O4 (LNMO) in Li-ion batteries strongly depends on its synthesis conditions, actual Ni/Mn stoichiometry, and degree of ordering of Ni and Mn. Depending on the extent of this ordering, the spinel structure can be described in the conventional space group Fd3¯m as the non-substituted LiMn2O4 or, for the highly ordered phase, in the space group P4332. As previously reported in the literature, using neutron and electron diffraction, a qualitative description of the extent of ordering can be achieved and roughly related to the electrochemical performance of LNMO. To deeper characterize and understand this complex system, in this paper, we will show that Raman spectroscopy, and especially the characteristics of the band located at 160 cm−1 attributed for the first time to a twisting motion of octahedral entities, allow to estimate the degree of ordering in LNMO, whereas NMR spectroscopy allows to give a clear description of the local environments of Li, in relationship with the Ni/Mn stoichiometry and extent of ordering. Theoretical calculations were used to support the analysis and attribution of the Raman and NMR signals/spectra. These spectroscopic characterizations enabled in-depth insights into the complexity of LNMO in stoichiometry, degree of ordering, and purity versus the presence of rock-salt or layered oxides as defects or crystalline domains.

Semi-wet synthesis of high-performance Li1.6Mn1.6O4 for selective lithium extraction from Salt Lakes Brine

Among the manganese-based lithium-ion sieves, Li1.6Mn1.6O4 has a high theoretical lithium adsorption capacity as a spinel ion sieve material. Small particle size orthogonal phase purity LiMnO2 powders were prepared by a semi-wet method and calcined in air at 400 °C to obtain Li1.6Mn1.6O4 a lithium-ion sieve precursor. The synergistic effects of oxygen atmosphere, heat treatment conditions and lithium/manganese molar ratio on the crystal structure of LiMnO2 and the lithium adsorption/desorption characteristics of Li1.6Mn1.6O4 were comprehensively investigated with XRD, SEM, TEM, XPS, Raman, DTA-TG and capacity retention study. Notably, when the initial lithium/manganese molar ratio was set at 1.1, and the sample underwent a calcination at 120 °C for 48 h under carefully controlled deoxygenation conditions, we observed the exclusive presence of the desired orthorhombic phase in the LiMnO2 sample. In contrast, when the synthesis conditions deviated from the optimized parameters led to the presence of the monoclinic phase of Li2MnO3. This highlights the sensitivity of Li1.6Mn1.6O4 properties to the synthesis conditions. The results of adsorption-desorption cycles show that the ion sieve Li1.6Mn1.6O4 prepared by heat treatment of ordered o-LiMnO2 is more stable, the structural stability of Li1.6Mn1.6O4 were characterized by high-temperature in-situ XRD experiments during heating from 30 to 800 °C. The equilibrium adsorption capacity was 34 mg g−1 in Qarhan Salt Lake brine at 10th cycle, and a remarkably low Mn dissolution loss rate of 0.6 %. The results have significant potential to advance the development of high-performance adsorbent in the Li-Mn-O system and contribute to the advances in lithium separation technology.