Synthesis Of Materials Research Articles

Solution combustion synthesis of zinc and calcium aluminate spinel phase materials: optical and structural properties

Solution combustion synthesis of zinc and calcium aluminate spinel phase materials: optical and structural properties

Synthesis of near-infrared-activated YF3:Yb3+, Tm3+/Bi2MoO6 upconversion photocatalytic materials for the photocatalytic degradation of antibiotics based on fluorescence resonance energy transfer

Photocatalytic degradation of pollutants, an ecofriendly technology, is widely used for environmental remediation. However, the design and synthesis of photocatalytic materials for near-infrared light photocatalysis are challenging. In this study, an upconversion photocatalyst with fluorescence resonance energy transfer (FRET), YF3:Yb3+, Tm3+/Bi2MoO6 (YFYT/BMO), was developed and synthesised based on rare-earth upconversion luminescence. YFYT converted near-infrared (NIR) light into blue–violet light via upconversion. The rapid decay of the fluorescence lifetime of YFYT/BMO at 478 nm (Tm3+:1G4-3H6) verified that FRET efficiently occurred between YFYT and BMO. The degradation rate of tetracycline by YFYT/BMO was 2.6 times higher than that by BMO under NIR light. A great enhancement of 42.1 % on the tetracycline degradation efficiency was achieved in YFYT/BMO compared with pure BMO within 90 min of visible-NIR irradiation. This study provides a basis for developing and designing rare-earth upconversion photocatalytic materials that can achieve excellent photocatalytic degradation of antibiotics using NIR light for environmental remediation.

Using industrial waste in porous building materials for indoor humidity control

This study uses waste bricks and waste catalyst as raw materials in the synthesis of humidity control building materials with high structural strength. This paper explores the feasibility of producing porous humidity control materials (PHCM) through the billet sintering of waste brick with various quantities of waste catalyst (0 %–40 %) for indoor construction. N2 adsorption and desorption isotherms revealed that PHCM exhibits Type-IV adsorption with H3 hysteresis loops, indicating a network of interconnected mesopores with diameters ranging from 3 to 17 nm. Humidity control analysis revealed that increasing the waste catalyst content significantly enhanced the equilibrium moisture content and moisture adsorption and desorption capacity. This study determined that the adsorption of moisture within the PHCM relies on capillary condensation within the mesopores. Under 95 % relative humidity (RH), the highest equilibrium moisture content (2.97 kg/kg) and 12-h moisture adsorption capacity (72.41 g/m2) were obtained in specimens prepared at a sintering temperature of 1000 °C with a 40 % spent catalyst. This excellent adsorption capacity can be attributed to the high surface area of the waste catalyst, which increased the surface area of PHCM from 0.013 to 8.529 m2/g. This study demonstrates the benefits of synthesizing PHCM using waste bricks and catalysts in terms of porous properties, mechanical properties, and humidity control performance.

Magnetostatic waves in metallic rectangular waveguides filled with uniaxial negative permeability media

The propagation characteristics of magneto-quasistatic waves, more commonly, known as magnetostatic waves in a long, metallic rectangular waveguide filled with a metamaterial slab are comprehensively investigated. The metamaterial slab consists of split-ring resonators as an anisotropic uniaxial medium with transversal negative effective permeability. Some analytical relations and numerical validations on the characteristics of these waves are presented. The results include the dispersion relations, mode patterns (field distributions) that can be supported by such media, and their corresponding cutoff frequencies, group velocities, power flows, and storage energies of magnetostatic waves. The findings from the present research study can be advantageous to advance the synthesis and development of negative permeability materials with peculiar features in guiding structures.

Proteomic Analysis of Arachis hypogaea Seeds from Different Maturity Classes.

Physiological maturity impacts seed quality through various mechanisms including vigor, desiccation tolerance, dormancy induction, synthesis of raw materials (including seed storage proteins), and the reorganization of metabolisms. Peanut seed development can be classified into seven classes with four incremental stages per class. Based on the mesocarp color, the final three stages are commonly referred to as "orange", "brown", and "black". In 2017, freshly harvested pods from one genotype of runner market-type peanuts grown under conventional practices were obtained from the University of Georgia research facility. The pods were removed from the plant material and 'pod blasted' to reveal the mesocarp. After separation, the remainder of the pod outer layer was removed, and the seeds were segregated for proteomic analysis. The raw peanuts were analyzed by bottom-up LC-MS/MS proteomics, which was conducted by the Proteomics Resource Center at the Rockefeller University, to identify the significant protein composition differences in each maturity class. The proteomic data revealed differentially expressed proteins as a function of maturity class with multiple functions including plant defense, metabolism, cell signaling, nutrient accumulation, and packaging. Understanding the processes needed for seed maturation will enable peanut scientists to evaluate the traits needed for robust germination, hardiness of the seed in response to disease, and nutrient quality.

High-capacity dilithium hydroquinone cathode material for lithium-ion batteries.

Lithiated organic cathode materials show great promise for practical applications in lithium-ion batteries owing to their Li-reservoir characteristics. However, the reported lithiated organic cathode materials still suffer from strict synthesis conditions and low capacity. Here we report a thermal intermolecular rearrangement method without organic solvents to prepare dilithium hydroquinone (Li2Q), which delivers a high capacity of 323 mAh g-1 with an average discharge voltage of 2.8V. The reversible conversion between orthorhombic Li2Q and monoclinic benzoquinone during charge/discharge processes is revealed by in situ X-ray diffraction. Theoretical calculations show that the unique Li-O channels in Li2Q are beneficial for Li+ ion diffusion. In situ ultraviolet-visible spectra demonstrate that the dissolution issue of Li2Q electrodes during charge/discharge processes can be handled by separator modification, resulting in enhanced cycling stability. This work sheds light on the synthesis and battery application of high-capacity lithiated organic cathode materials.

Facile Synthesis and Electrochemical Analysis of Zn-Doped V2O5 Anode Materials for High-Rate Li Storage

The surging demand for Li rechargeable batteries with high energy densities and rapid rate capability has propelled research on materials that can replace the conventional anode materials like graphite. Vanadium pentoxides (V2O5) have emerged as promising anode candidates owing to their excellent rate capability. Specifically, V2O5 allows the electrochemical prelithiation process, in which three Li-ions can be inserted to form Li3V2O5, followed by reversible insertion and extraction of two Li-ions. Nevertheless, the unsatisfactory Li-ion diffusion coefficients and electrical conductivities of these materials remain major drawbacks. Here, we propose a Zn-doped V2O5 anode, fabricated using a two-step sol–gel method, for high-rate Li-ion batteries. Zn was incorporated into V2O5 to enhance the Li-ion transport kinetics through the electrode. The crystal structure (orthorhombic) of Zn-doped V2O5 was identified by X-ray diffraction analysis, and the Zn doping was confirmed by X-ray photoelectron microscopy. The effect of Zn doping was thoroughly examined using various analytical methods, such as cyclic voltammetry and galvanostatic intermittent titration technique. The Zn-doped V2O5 electrode exhibited remarkable cycling durability, enduring for 1000 cycles, while retaining an enhanced capacity, even under a high rate of 2C.

Synthesis and Properties of the LiMn2O4 Cathode Material for Lithium-ion Batteries

Spinel LiMn2O4 was synthesized by high-temperature solid-state method with lithium salt and manganese salt as raw materials, which were mixing with anhydrous ethanol as solvent under stirring, and calcining at high temperature in in the oxygen atmosphere. X-ray diffraction (XRD) and scanning electron microscope (SEM) showed that the size of lithium manganese particles with spinel structure was 80 to 200 nm, and the particle size distribution was uniform. The results showed that the prepared LiMn2O4 sample sintered at 700°C exhibited superior electrochemical performance when used as a cathode material for lithium-ion batteries with a voltage window of 2.5–4.8 V. The first charge-discharge specific capacity and first discharge capacity can reach 158.0 mAh‧g-1 and 138.4 mAh‧g-1, respectively, at 0.1 A‧g-1 current density, and the first Coulomb retention efficiency is 87.6%. The discharge specific capacity of the LiMn2O4 material can be maintained at 114 mAh‧g-1 when the test current density was returned to 0.1 A‧g-1 after 60 cycles.

Enhancing Intramolecular Ferromagnetic Coupling in Tetrathiafulvalene-Nitronyl Nitroxide-Based Compounds through Spin Polarization Mechanism.

Spin-polarized donor radicals based on tetrathiafulvalene (TTF) derivatives and nitronyl nitroxide (NN) radicals in which one-electron oxidation involves the HOMO instead of the SOMO are well known for exhibiting magnetoresistance. In particular, BTBN consists of one dibromo-TTF and one NN radical, which are linked by a phenyl coupler group. One of the key factors driving magnetoresistance is the presence of intramolecular ferromagnetic (FM) coupling between the oxidized π-donor (TTF+⋅, D unit) and NN (R unit). Here, a theoretical study is carried out to assess suitable candidates with enhanced FM coupling with respect BTBN, which is thus used as a reference. The study is conducted via in silico chemical modification of the substituents of the BTBN basic functional units (D and R radicals, C coupler) to benefit from the spin polarization mechanism to boost the intramolecular FM coupling, aiming to distort the BTBN radical arrangement within the molecular crystal as little as possible, in the event the material can be synthesized. NICSiso(1) and Wiberg's Bond Order are analyzed to further assist in identifying promising potential candidates, since the decrease in aromaticity is expected to enhance the diradical character and give rise to a larger magnetic coupling value. The most favorable diradical building block to replace the BTBN moiety results from using a hydroxyl-ethylene (-(H)C=C(OH)-) as a coupler preserving BTBN original radicals, namely, NN and TTF+⋅ units. This study aims at illustrating the feasibility of improving the intramolecular FM interaction between radical moieties, which is fully realized, as a first step towards the synthesis of new materials with (possibly) enhanced magnetoresistance properties.

Electronic structure and effective mass of pristine and Cl-doped CsPbBr3

Organic–inorganic lead halide perovskites (LHPs) have attracted great interest owing to their outstanding optoelectronic properties. Typically, the underlying electronic structure would determinate the physical properties of materials. But as for now, limited studies have been done to reveal the underlying electronic structure of this material system, comparing to the huge amount of investigations on the material synthesis. The effective mass of the valance band is one of the most important physical parameters which plays a dominant role in charge transport and photovoltaic phenomena. In pristine CsPbBr3, the Fröhlich polarons associated with the Pb–Br stretching modes are proposed to be responsible for the effective mass renormalization. In this regard, it would be very interesting to explore the electronic structure in doped LHPs. Here, we report high-resolution angle-resolved photoemission spectroscopy (ARPES) studies on both pristine and Cl-doped CsPbBr3. The experimental band dispersions are extracted from ARPES spectra along both Γ¯ – M¯ – Γ¯ and X¯ – M¯ – X¯ high symmetry directions. DFT calculations are performed and directly compared with the ARPES data. Our results have revealed the band structure of Cl-doped CsPbBr3 for the first time, which have also unveiled the effective mass renormalization in the Cl-doped CsPbBr3 compound. Doping dependent measurements indicate that the chlorine doping could moderately tune the renormalization strength. These results will help understand the physical properties of LHPs as a function of doping.

Bimetallic Organic Frameworks via In Situ Solvothermal Sol-Gel-Crystal and Sol-Crystal Transformation as Durable Electrocatalysts for Oxygen Reduction Reaction.

The in situ solvothermal conversion of metal-organic gels (MOGs) to crystalline metal-organic frameworks (MOFs) represents a versatile and ingenious strategy that has been employed for the synthesis of MOF materials with specific morphologies, high yield, and improved functional properties. Herein, we have adopted an in situ solvothermal conversion of bimetallic MOGs to crystalline bimetallic MOFs with the aim of introducing a redox-active metal heterogeneity into the monometallic counterpart. The formation of bimetallic NiZn-MOF and CoZn-MOF via in situ solvothermal sol-gel-crystal and sol-crystal transformation is found to depend on the solvent systems used. The sol-to-gel-to-crystal transformation of NiZn-MOF via the formation of NiZn-MOG is found to occur through the gradual disruption of gel fibers leading to subsequent formation of microcrystals and single crystals of NiZn-MOF. These bimetallic MOFs and MOGs serve as promising electrocatalysts for oxygen reduction reaction (ORR) with an excellent methanol tolerance property, which can be attributed to the enhanced mass and charge transfer, higher oxygen vacancies, and bimetallic synergistic interactions among the heterometals. This work demonstrates a convenient strategy for producing bimetallic MOGs to MOFs through the introduction of a redox-active metal heterogeneity in the inorganic hybrid functional materials for fundamental and applied research. Our results connect MOGs and MOFs which have been regarded as having opposite physical states, that is, soft vs hard, and provide promising structural correlation between MOGs and MOFs at the molecular level.

Rapid conformational analysis of semi-flexible liquid crystals

ABSTRACT We present an approach for rapid conformational analysis of semi-flexible liquid crystals. We use a simple graphical user interface (GUI) tool that leverages rules-based methods for efficient generation of bend-angle distributions, offering a significant improvement over traditional single-conformer analysis. Our methods demonstrated proficiency in approximating molecular shapes comparable to those obtained from molecular dynamics (MD) simulations, albeit with notable deviations in the under sampling of hairpin conformations and oversampling of extended configurations. Re-evaluation of existing data revealed an apparent weak correlation between NTB transition temperatures and bend angles, underscoring the complexity of molecular shapes beyond mere geometry. Furthermore, we integrated this conformational analysis into a pipeline of algorithmic molecular design, utilising a fragment-based genetic algorithm to generate novel cyanobiphenyl-containing materials. This integration opens new avenues for the exploration of liquid crystalline materials, particularly in systems where systematic conformer searches are impractical, such as large oligomeric systems. Our findings highlight the potential and growing importance of computational approaches in accelerating the design and synthesis of next-generation liquid crystalline materials.

Synthesis of coal slime-based catalytic material for peroxymonosulfate activation through molten salt thermal treatment

Coal slime-based peroxymonosulfate (PMS) catalytic materials were synthesized utilizing coal slime (CS) as raw material under the N2 atmosphere in this study. Raw and calcined coal slime were systematically characterized concerning morphologies, pore structures, chemical bonds, phase constituents, and defect density. Results show that after being calcinated with FeCl2∙4H2O at 750 °C, the specific surface area increased by nearly 21.0 times higher than that of CS. The addition of FeCl2∙4H2O has certain effect on the chemical bonds of calcined coal slime, i.e. the Fe elements can be fixed by the silicon aluminum skeleton with sekaninaite (Fe2Al4Si5O18) and aluminum iron silicon (Al0.5Fe3Si0.5, above 650 °C) generation, and the ID/IG values increase to 2.96 for CS-FeCl2-750. In addition, the degradation percentage of phenol by using CS-FeCl2 can achieve 100% in 25 min under optimized conditions. Furthermore, 1O2 plays a major role in phenol degradation, followed by •OH and SO4•− in the CS-FeCl2/PMS system from the quenching experiments and electron paramagnetic resonance results. Overall, the novel CS-FeCl2 material displays good application prospects in the field of effluent treatment, with efficient utilization of carbonaceous and silicon aluminum skeleton in coal slime.

Rechargeable Metal-Sulfur Batteries: Key Materials to Mechanisms.

Rechargeable metal-sulfur batteries are considered promising candidates for energy storage due to their high energy density along with high natural abundance and low cost of raw materials. However, they could not yet be practically implemented due to several key challenges: (i) poor conductivity of sulfur and the discharge product metal sulfide, causing sluggish redox kinetics, (ii) polysulfide shuttling, and (iii) parasitic side reactions between the electrolyte and the metal anode. To overcome these obstacles, numerous strategies have been explored, including modifications to the cathode, anode, electrolyte, and binder. In this review, the fundamental principles and challenges of metal-sulfur batteries are first discussed. Second, the latest research on metal-sulfur batteries is presented and discussed, covering their material design, synthesis methods, and electrochemical performances. Third, emerging advanced characterization techniques that reveal the working mechanisms of metal-sulfur batteries are highlighted. Finally, the possible future research directions for the practical applications of metal-sulfur batteries are discussed. This comprehensive review aims to provide experimental strategies and theoretical guidance for designing and understanding the intricacies of metal-sulfur batteries; thus, it can illuminate promising pathways for progressing high-energy-density metal-sulfur battery systems.

Utilizing Waste Cotton/Pigeon Pea Stalk Fibers Composites for Enhanced Sound Absorption and Insulation in Automotive Interiors

ABSTRACT This study investigates the synthesis and characterization of composite materials, pigeon pea stem, and cotton fibers blended in different ratios such as 100/0, 70/30, 60/40, 50/50, 30/70, and 0/100. These composite materials were produced using a compression molding technique. According to ASTM standards, the acoustics, thermal conductivity, and physical characteristics of the composite samples were tested to assess their qualities. The impedance tube method detailed in ASTM E1050 was used to determine the sound absorption coefficients (SAC) for acoustics. The SAC values were measured at six frequencies such as 125, 250, 500, 1000, 2000, and 4000 Hz. The results showed that composite samples made from waste cotton and pigeon pea demonstrated sound absorption values of greater than 80%. Superior sound insulation and absorption, moisture absorption, fiber properties have also been demonstrated by waste composites. Especially, the waste cotton/pea stalk waste fiber composites achieved over 75% sound absorption, while the waste 28% composites performed well in terms of sound absorption, moisture absorption, and fiber properties. Even in humid conditions, the composite samples constructed from used cotton and pigeon pea stalks demonstrated good moisture resistance without reducing their insulating qualities. Soundproofing barriers are composite layers of foam or pigeon pea/cotton.

Synthesis and Characterization of a Photocatalytic Material from TiO2 Nanoparticles Supported on Zeolite Obtained from Ignimbrite Residue Used in Decolorization of Methyl Orange

In the present work, a TiO2/zeolite photocatalyst was synthesized by dispersing TiO2 nanoparticles obtained through the sol-gel method onto the surface of natural zeolite derived from ignimbrite residue. The zeolite was obtained from an ignimbrite rubble treatment collected from a quarry in Arequipa City, Peru. The research focused on the effect of zeolite on the TiO2 nanoparticles. The synthesized photocatalysts were characterized using various techniques, including field-emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray (EDS), X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), and Brunauer–Emmett–Teller surface area analysis (BET). The results revealed that the TiO2/zeolite samples displayed high crystallinity, with TiO2 being present in three phases and zeolite being present in the analcime phase. Furthermore, these samples exhibited a band gap of 3.14 eV and a high surface area compared to that of bare TiO2. Finally, the photocatalytic activity of the TiO2/zeolite composite obtained was evaluated toward the decomposition of 10 ppm and 20 ppm of methyl orange (MO) dye. The TiO2/zeolite samples demonstrated improved photocatalytic activity compared to that of pristine TiO2 under the same experimental conditions. This enhancement is primarily attributed to the increased specific surface area of the TiO2/zeolite samples, making them promising materials for future efficient and sustainable photocatalytic applications.

Single-atomic-Ni electrocatalyst derived from phthalocyanine-modified MOF for convoying CO2 intelligent utilization

Single-atomic-site catalysts have been demonstrated as promising candidates for electrochemical CO2 reduction reaction (eCO2RR). However, the universal construction strategies need to be further developed to synthesize the desired single-atomic-site catalysts with high eCO2RR activity for feasible CO2 utilization. Herein, a novel 2-methylimidazole-phthalocyanine-Ni (IM4NiPc) coordinatively modified ZIF-8 was rationally fabricated and applied to derive the single-atomic-Ni electrocatalyst (Ni-N-C-l), which is capable of delivering much improved activity for eCO2RR, compared to the pristine IM4NiPc immobilized onto ZIF-8-derived N-doped carbon surface, and is also comparable to the best reported catalysts. The satisfied Faradaic efficiency, current density and stability of CO2-to-CO electroconversion over Ni-N-C-l are shown to originate from the verified Ni-N4 configuration, particularly, reaching a CO Faradaic efficiency of 99% in a wide potential range. Moreover, based on the outstanding eCO2RR activity of Ni-N-C-l, we successfully realized the exemplary synthesis of amide polymer materials through CO-mediated electro/thermocatalytic cascade processes, demonstrating the feasibility of utilizing CO2 for material manufacturing. This finding is expected to provide useful insight on the precise design and rational synthesis of the novel single-atomic-site catalysts for future CO2 intelligent utilization.

Zeolitic imidazolate framework-8: a versatile nanoplatform for tissue regeneration.

Extensive research on zeolitic imidazolate framework (ZIF-8) and its derivatives has highlighted their unique properties in nanomedicine. ZIF-8 exhibits advantages such as pH-responsive dissolution, easy surface functionalization, and efficient drug loading, making it an ideal nanosystem for intelligent drug delivery and phototherapy. These characteristics have sparked significant interest in its potential applications in tissue regeneration, particularly in bone, skin, and nerve regeneration. This review provides a comprehensive assessment of ZIF-8's feasibility in tissue engineering, encompassing material synthesis, performance testing, and the development of multifunctional nanosystems. Furthermore, the latest advancements in the field, as well as potential limitations and future prospects, are discussed. Overall, this review emphasizes the latest developments in ZIF-8 in tissue engineering and highlights the potential of its multifunctional nanoplatforms for effective complex tissue repair.

Navigating phase diagram complexity to guide robotic inorganic materials synthesis

Efficient synthesis recipes are needed to streamline the manufacturing of complex materials and to accelerate the realization of theoretically predicted materials. Often, the solid-state synthesis of multicomponent oxides is impeded by undesired by-product phases, which can kinetically trap reactions in an incomplete non-equilibrium state. Here we report a thermodynamic strategy to navigate high-dimensional phase diagrams in search of precursors that circumvent low-energy, competing by-products, while maximizing the reaction energy to drive fast phase transformation kinetics. Using a robotic inorganic materials synthesis laboratory, we perform a large-scale experimental validation of our precursor selection principles. For a set of 35 target quaternary oxides, with chemistries representative of intercalation battery cathodes and solid-state electrolytes, our robot performs 224 reactions spanning 27 elements with 28 unique precursors, operated by 1 human experimentalist. Our predicted precursors frequently yield target materials with higher phase purity than traditional precursors. Robotic laboratories offer an exciting platform for data-driven experimental synthesis science, from which we can develop fundamental insights to guide both human and robotic chemists.

Artificial Intelligence Driving Materials Discovery? Perspective on the Article: Scaling Deep Learning for Materials Discovery.

The discovery of new crystalline inorganic compounds-novel compositions of matter within known structure types, or even compounds with completely new crystal structures-constitutes an important goal of solid-state and materials chemistry. Some fractions of new compounds can eventually lead to new structural and functional materials that enhance the efficiency of existing technologies or even enable completely new technologies. Materials researchers eagerly welcome new approaches to the discovery of new compounds, especially those that offer the promise of accelerated success. The recent report from a group of scientists at Google who employ a combination of existing data sets, high-throughput density functional theory calculations of structural stability, and the tools of artificial intelligence and machine learning (AI/ML) to propose new compounds is an exciting advance. We examine the claims of this work here, unfortunately finding scant evidence for compounds that fulfill the trifecta of novelty, credibility, and utility. While the methods adopted in this work appear to hold promise, there is clearly a great need to incorporate domain expertise in materials synthesis and crystallography.