Synthesis Of Materials Research Articles

Performance and mechanism of antibiotic resistance removal by biochar-enhanced sediment microbial fuel cell

This study is the first to explore the performance and mechanism of biochar-impacted sediment microbial fuel cell for removing antibiotic resistance genes (ARGs), and examines the effects of different biochar contents. The addition of 5% biochar produced the highest output voltage and power density, which increased by 100% and 219%, respectively, while simultaneously reducing the abundance and risk of ARGs. Comparatively, the addition of moderate amount of biochar (1–5%) promoted the removal of ARGs, while the opposite was true for excessive (10%) biochar. Biochar affected ARGs through prophages, insertion sequence, and transposons. Biological factors and voltage jointly influenced ARGs variation, with the former accounting for 56%. Further analysis of functional genes indicated that biochar controlled ARGs by regulating the synthesis of genetic material and amino acids to influence metabolism. Overall, findings of this study shed light on the potential removal of ARGs in microbial electrochemical systems.

Energetic Methylene-Bridged Furoxan-Triazole/Tetrazole Hybrids.

Design and synthesis of new energetic materials retains its urgency in chemistry and materials science. Herein, rational construction and regioselective synthesis of a series of energetic compounds comprising of a methylene-bridged combination of 1,2,5-oxadiazole and nitrogen-rich azoles (1,2,4-triazole and tetrazole) enriched with additional explosophoric functionalities (nitro and azo moieties) is presented. All target materials were thoroughly characterized using IR and multinuclear NMR (1H,13C,14N,15N) NMR spectroscopy, high-resolution mass spectrometry, X-ray diffraction,and differential scanning calorimetry. All synthesized energetic substances showed good thermal stability (up to 239oC) and low mechanical sensitivity, while their performance reached or exceeded the level of TNT.

Quantum Chemical Stability Analysis of Phthalocyanine Metal One-Dimensional Polymers with Bidentate Ligands.

The combination of metal-phthalocyanine complexes and axially coordinated organic molecules into polymer chains presents a significant challenge in the synthesis of hybrid materials. A calculated structure for one-dimensional coordinate polymers with N-donor ligands using ab initio (PM6) and DFT (LanL2Dz) methods is presented. DFT methods have shown that there is a linear, one-dimensional structure without distorted geometry for the two bipyridine ligands. The components of the proposed polymers consist of square-planar Zn complexes of phthalocyanine (PcZn) connected via bridging ligands (L). Electronic properties of the monomer PcZnL of zinc phthalocyanine with bidentate ligands have been analyzed using calculations based on density functional theory (B3LYP6-31G(d,p)). Molecular orbital calculations show that this connection between the metallomacrocycle and the conjugated ligand results in a small energy gap, promising molecularly active materials as conductors. The crystallographic reports indicate that obtaining this kind of polymer with the participation of Pc Zn and bidentate ligands is possible.

One-step synthesis of Pt@(CrMnFeCoNi)3O4 high entropy oxide catalysts through flame spray pyrolysis

High entropy oxides (HEOs) show great prospects in catalysis owing to their widely tunable component structures and ease of combination with active metals. However, the development of HEO catalysts is limited by the lack of efficient synthesis methods due to the difficulty of homogeneously mixing at least five elements. In this work, flame spray pyrolysis (FSP) is successfully employed to synthesize (CrMnFeCoNi)3O4 HEO with a single phase spinel structure in one step, which is verified by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), and energy-dispersive X-ray spectroscopy (EDS). Taking CO catalytic oxidation as a probe reaction, the Pt@(CrMnFeCoNi)3O4 HEO catalyst synthesized by FSP in one step is compared with the catalyst whose Pt is impregnated on (CrMnFeCoNi)3O4 HEO support. The FSP-made catalysts have a higher catalytic reaction rate and better redox ability, which lowers the temperature of complete CO conversion by nearly 100 °C. Furthermore, it can be observed that the flame parameters can be optimized to modify the particle size and oxygen vacancies of the HEO nanoparticles, thus enhancing the catalytic performances. This work demonstrates that FSP is an effective method for the one-step synthesis of HEO catalysts with excellent catalytic performance, providing a new perspective for the synthesis of HEO-based materials.

Exploration of adsorption properties of organic corrosion inhibitors on layered double hydroxide nanosheet: A molecular dynamics simulation study

Understanding the adsorption of organic corrosion inhibitors with different functional groups on layered double hydroxide (LDH) nanosheet is crucial for the synthesis of these protective materials. In this study, the adsorption process of five deprotonated organic corrosion inhibitors—lactate (Lc), 2-hydroxybenzothiazole (2-OH-BTH), 2-mercaptoethanesulfonic acid (MS), N,N-dimethylethanolamine (DMEA), and eugenol (EG)—on LDH nanosheets was simulated. The adsorption rate, adsorption configuration, and adsorption stability between LDH nanosheet and organic corrosion inhibitors were investigated throughout the entire adsorption process. The study observed consistency in the adsorption rate and stability of these organic corrosion inhibitors in the following order: Lc > 2-OH-BTH > MS > DMEA > EG. Additionally, hydrogen bonds between the organic corrosion inhibitors and the LDH nanosheet is the primary mechanism driving adsorption. The number and stability of hydrogen bonds influenced both the adsorption rate and stability. It is noteworthy that 2-OH-BTH and DMEA have not previously been incorporated into LDH. There is potential for these two organic corrosion inhibitors to be modified for LDH, suggesting significant prospects for future research.

Novel one-pot synthesis of nitrogen-containing derivatives via C-N bond formation and C-O bond cleavage

Ortho-aminophenols are significant organic compounds known for their versatility and wide-ranging applications in materials science, synthesis, pharmaceuticals, agriculture, and industry. In this work, we present novel synthetic methods that utilize readily available and cost-effective materials, namely catechol, Cd(NO3)2 as a catalyst, and H2O/EtOH solvent. These proposed synthesis methods involve mild, one-pot reactions that facilitate the formation of both C-N and cleavage of C-O bond. This approach leads to the production of various nitrogen-containing derivatives with remarkably high yields and efficiency.

Hard carbon/graphene microfibers as a superior anode material for sodium-ion batteries

Hard carbon is one of the most promising anode materials for sodium-ion batteries (SIBs). However, it still suffers from low specific capacity and poor rate capability, which impede its practical application. Herein, one-dimensional hard carbon/graphene microfibers are synthesized by encapsulating hard carbon particles in graphene nanosheet using a wet-spinning technique followed by pyrolysis treatment. Benefiting from the unique structure, when used as the anode material for SIBs, the as-obtained hard carbon/graphene microfibers not only exhibit a high reversible capacity of 321 mAh g−1 at 0.1 C but also deliver long cycling stability and excellent rate capability, maintaining its capacity as 203 mAh g−1 even after 350 cycles at 1 C. In addition, the sodium storage mechanism of the as-prepared hard carbon/graphene microfibers is investigated by in-situ Raman technique. Moreover, a full cell adopting the hybrid microfiber as the anode and Na3V2(PO4)3 as the cathode exhibits high specific capacities of 291 mAh g−1 and 204 mAh g−1 at 0.2 C and 4 C (vs. anode), respectively. This work provides a sustainable and cost-effective strategy for the synthesis of high-capacity and stable hard carbon anode materials.

One-pot radiolytically synthesized reduced graphene oxide-gold nanoparticles composites and exploration in energy storage

Graphene and its composites are of primary importance, particularly in the field of energy storage. Numerous bottom-up and top-down methods have been proposed in the literature to produce these materials with enhanced physicochemical properties. Recently, an innovative and green methodology was developed based on ionizing radiation, allowing the quantitative synthesis of graphene oxide-based materials. With the aim to extend this strategy for the preparation of hybrid nanomaterials, the objective of this work was the one-pot synthesis of nanocomposites composed of reduced graphene oxide – gold nanoparticles (rGO-AuNPs) via gamma ray-induced radiolytic reduction. UV–Vis Absorption Spectroscopy, Fourier Transform Infrared Spectroscopy, Raman Spectroscopy and X-ray Photoemission Spectroscopy were utilized to comprehensively evaluate the reduction degree of graphene oxide and the formation of gold nanoparticles. Atomic Force Microscopy and Scanning Electron Microscopy were employed to obtain the morphological and topographical information on synthesized nanocomposites. Thermal properties were investigated by Thermogravimetric Analysis and electrical properties were investigated using Cyclic Voltammetry and Potentiostatic Charge and Discharge method. The results demonstrated the successful reduction of graphene oxide and gold ions through the drastic transformation of oxygen-containing functional groups and the formation of gold nanoparticles. Electrical characterization results highlighted the excellent electrical properties of radiosynthesized rGO-AuNPs composites and their great potential for supercapacitance application.

Radiative heat recuperation in combustion of layered solid fuel

In this work, we investigate the properties and stability of the combustion waves propagating in a system of layered solid fuel material in which the neighbouring fuel sheets can recuperate heat via thermal electromagnetic radiation. The analysis is undertaken within the flame sheet model, which allows to determine the combustion wave speed and structure and derive the dispersion relation characterising the stability of the reaction front. The proper choice of parameters leads to superadiabatic combustion temperature and significant increase of the combustion wave speed. In addition, the stable steady regimes of combustion can be substantially extended in the space of parameters. Such an enhancement of stability and ability to control the characteristics of the combustion wave propagation can be very attractive for the combustion synthesis of new layered materials, similarly to the chemical furnace technology proposed earlier.

Calcium Manganite Based Materials for Thermochemical Energy Storage in High Temperature Solar Thermal Plants: Materials Screening

The urgent need for sustainable energy supply requires maximum exploitation of renewable energy sources. The latter, being of intermittent nature, need to be coupled with efficient energy storage. Solar-thermal power-plants are inherently compatible with thermal storage, which is a cost-efficient method of storing energy for later use but the field is currently dominated by sensible heat molten salts used as heat storage media but with a maximum operating temperature of about 560oC. Certain ceramic materials, able to induce reversible reduction-oxidation reactions under air flow, are promising alternatives to molten salts because they can withstand much higher temperatures (>1000oC) and thus can be integrated with high-efficiency air-Brayton thermodynamic cycles. At the same time the chemical energy stored/released during such reduction-oxidation reactions can boost energy storage density by up to 10 times cf. sensible only concepts. In this framework, Ca-Mn-based perovskite compositions were demonstrated to function effectively as energy storage materials. The current work offers insights on material synthesis parameters to achieve relatively high purity Ca-Mn-based compositions and subsequently optimize their redox performance in the course of a preliminary 5-cycle campaign. Moreover, the occurring structural transitions and their corresponding heat effects are also discussed and elaborated upon. This study is the first step towards the, currently in progress, process of synthesising – at multi kg scale – and shaping these compositions into extruded honeycomb-like monolithic structures for subsequent future application in lab- and pilot-scale high temperature thermochemical energy storage systems.

Cation-eutaxy-enabled III-V-derived van der Waals crystals as memristive semiconductors.

Novel two-dimensional semiconductor crystals can exhibit diverse physical properties beyond their inherent semiconducting attributes, making their pursuit paramount. Memristive properties, as exemplars of these attributes, are predominantly manifested in wide-bandgap materials. However, simultaneously harnessing semiconductor properties alongside memristive characteristics to produce memtransistors is challenging. Herein we prepared a class of semiconducting III-V-derived van der Waals crystals, specifically the HxA1-xBX form, exhibiting memristive characteristics. To identify candidates for the material synthesis, we conducted a systematic high-throughput screening, leading us to 44 prospective III-V candidates; of these, we successfully synthesized ten, including nitrides, phosphides, arsenides and antimonides. These materials exhibited intriguing characteristics such as electrochemical polarization and memristive phenomena while retaining their semiconductive attributes. We demonstrated the gate-tunable synaptic and logic functions within single-gate memtransistors, capitalizing on the synergistic interplay between the semiconducting and memristive properties of our two-dimensional crystals. Our approach guides the discovery of van der Waals materials with unique properties from unconventional crystal symmetries.

Wafer‐scale single‐crystal two‐dimensional materials for integrated optoelectronics

AbstractSince the pioneering research on graphene, two‐dimensional (2D) materials have been considered as the most promising candidates to continue advancing Moore's Law, and an emerging material family, which has bred a lot of novel functional applications beyond the Si‐based integrated circuit. Unfortunately, abundant challenges in the synthesis of wafer‐scale single‐crystal (WSSC) 2D materials and their on‐chip integration technology severely hinder their commercialization road. Over the past few years, significant technique breakthroughs of WSSC 2D materials have been increasingly achieved, accordingly a comprehensive review and critical evaluation of these new advances are pressingly required. In this review article, the outstanding research progress on the synthesis of WSSC 2D materials and 2D material‐based on‐chip integration technology, including 2D materials integration, nanopatterning, electrode integration, and dielectric integration, are summarized in detail. Then, the major application prospect of different types of WSSC 2D materials in optoelectronics is discussed. Finally, a critical assessment of these advancements is given, as well as the potential challenges and opportunities in the foreseeable future.

Synthesis of mixed-base active material from drilling fluid solid waste and biomass for oil wastewater adsorption and its mechanism

To address the issues of high energy consumption, high cost and the risk of secondary pollution in drilling fluid solid waste treatment methods, this study prepared a mixed-based active material using drilling fluid solid waste and biomass materials as raw materials. The mixed-based active material is characterized by its abundant pore structure and high pore volume, demonstrating excellent adsorption performance for heavy metal ions and residual oil in industrial wastewater. Thermogravimetric and basic physical property analyses indicated a synergistic effect between drilling fluid solid waste and biomass materials, showing that joint pyrolysis of the two can enhance the yield of active materials. The adsorption performance of mixed-base active materials for heavy metal ions and residual oil were was tested. It was found that the removal rate of four heavy metal ions (Cr6+, Mn2+, Cu2+, and Zn2+) from the solution could reached 57.1 %, 96.3 %, 99.0 % and 94.1 %, respectively, at a concentration of 0.5 g/L of mixed-base active materials. Characterization revealed that the mixed-base activated carbon has a well-developed pore structure and numerous types of functional groups. The isothermal adsorption process of heavy metal ions by the active material is consistent with the Langmuir model and belongs to the monomolecular layer adsorption. The adsorption rate model of residual oil in wastewater by active materials conforms to the pseudo-second-order equation. The adsorption performance of mixed-base active materials primarily stems from physical adsorption enabled by their well-developed internal pore structure, along with chemical adsorption facilitated by oxygen- and nitrogen-containing functional groups on the surface.

Resources, energy consumption and economic analysis for flame synthesis of ternary cathode materials

Cathode materials account for around one third of the manufacturing cost of lithium-ion battery, which are the major factor preventing the wider applications of power battery packs. Flame synthesis (FS) is a new manufacturing technology of nanostructured materials with few equipment and high efficiency, which potentially can substantially bring down the manufacturing cost of cathode materials. The primary objective of the present study was to quantitatively evaluate the resources, energy consumption and economic feasibility of large-scale production of cathode materials though FS. In the analysis process, the mass flow of reactants and resultants as well as the minimum cathode material selling price (MCSP) of ternary cathode material LiNixCoyMn(1-x-y)O2 (x + y + z = 1) produced by FS were calculated, and compared with that of the conventional hydroxide co-precipitation method. Results show that the production of ternary cathode material through FS can reduce CO2 emissions by ∼60% and water consumption by ∼30%. MCSP of LiNi0.5Co0.2Mn0.3O2 (NCM523), LiNi0.6Co0.2Mn0.2O2 (NCM622), and LiNi0.8Co0.1Mn0.1O2 (NCM811) produced by FS are 224.8 k¥/t, 235.1 k¥/t, 240.0 k¥/t, which respectively are about 2%, 10% and 14% lower than the average selling prices in Chinese market, indicating that FS is economically feasible for producing ternary cathode materials. Particularly, for the production of high-nickel cathode materials, FS has notable potential in simplifying the production process and manufacturing costs. Sensitivity analysis of NCM811 produced by FS shows that when raw material price, fuel and power costs are reduced by 25%, MCSP can be as low as 186.4 k¥/t. When the metal cation concentration of the solution increases to 3.2 mol/L, it enables FS to meet the most rigorous energy consumption limitation standards in China. When the lithium excess is reduced from 10% to 5%, MCSP of NCM811 can be further reduced by 5.6 k¥/t, indicating that lithium loss due to high temperatures in FS is a moderate factor for reducing the manufacturing cost. Finally, this work presents a life cycle assessment (LCA) of NCM materials produced by FS in China. Comparison to the global warming potential (GWP) of the co-precipitation method in the literature indicated that GWP of FS is lower.

A metastable pentagonal 2D material synthesized by symmetry-driven epitaxy.

Most two-dimensional (2D) materials experimentally studied so far have hexagons as their building blocks. Only a few exceptions, such as PdSe2, are lower in energy in pentagonal phases and exhibit pentagons as building blocks. Although theory has predicted a large number of pentagonal 2D materials, many of these are metastable and their experimental realization is difficult. Here we report the successful synthesis of a metastable pentagonal 2D material, monolayer pentagonal PdTe2, by symmetry-driven epitaxy. Scanning tunnelling microscopy and complementary spectroscopy measurements are used to characterize this material, which demonstrates well-ordered low-symmetry atomic arrangements and is stabilized by lattice matching with the underlying Pd(100) substrate. Theoretical calculations, along with angle-resolved photoemission spectroscopy, reveal monolayer pentagonal PdTe2 to be a semiconductor with an indirect bandgap of 1.05 eV. Our work opens an avenue for the synthesis of pentagon-based 2D materials and gives opportunities to explore their applications such as multifunctional nanoelectronics.

High Efficiency Removal Performance of Tetracycline by Magnetic CoFe2O4/NaBiO3 Photocatalytic Synergistic Persulfate Technology.

The widespread environmental contamination resulting from the misuse of tetracycline antibiotics (TCs) has garnered significant attention and study by scholars. Photocatalytic technology is one of the environmentally friendly advanced oxidation processes (AOPs) that can effectively solve the problem of residue of TCs in the water environment. This study involved the synthesis of the heterogeneous magnetic photocatalytic material of CoFe2O4/NaBiO3 via the solvothermal method, and it was characterized using different characterization techniques. Then, the photocatalytic system under visible light (Vis) was coupled with peroxymonosulfate (PMS) to explore the performance and mechanism of degradation of tetracycline hydrochloride (TCH) in the wastewater. The characterization results revealed that CoFe2O4/NaBiO3 effectively alleviated the agglomeration phenomenon of CoFe2O4 particles, increased the specific surface area, effectively narrowed the band gap, expanded the visible light absorption spectrum, and inhibited recombination of photogenerated electron-hole pairs. In the Vis+CoFe2O4/NaBiO3+PMS system, CoFe2O4/NaBiO3 effectively activated PMS to produce hydroxyl radicals (·OH) and sulfate radicals (SO4-). Under the conditions of a TCH concentration of 10 mg/L-1, a catalyst concentration of 1 g/L-1 and a PMS concentration of 100 mg/L-1, the degradation efficiency of TCH reached 94% after 100 min illumination. The degradation of TCH was enhanced with the increase in the CoFe2O4/NaBiO3 and PMS dosage. The solution pH and organic matter had a significant impact on TCH degradation. Notably, the TCH degradation efficiency decreased inversely with increasing values of these parameters. The quenching experiments indicated that the free radicals contributing to the Vis+CoFe2O4/NaBiO3+PMS system were ·OH followed by SO4-, hole (h+), and the superoxide radical (O2-). The main mechanism of PMS was based on the cycle of Co3+ and Co2+, as well as Fe3+ and Fe2+. The cyclic tests and characterization by XRD and FT-IR revealed that CoFe2O4/NaBiO3 had good degradation stability. The experimental findings can serve as a reference for the complete removal of antibiotics from wastewater.

Assembly of Differently Sized Supercharged Protein Nanocages into Superlattices for Construction of Binary Nanoparticle-Protein Materials.

This study focuses on the design and characterization of binary nanoparticle superlattices: Two differently sized, supercharged protein nanocages are used to create a matrix for nanoparticle arrangement. We have previously established the assembly of protein nanocages of the same size. Here, we present another approach for multicomponent biohybrid material synthesis by successfully assembling two differently sized supercharged protein nanocages with different symmetries. Typically, the ordered assembly of objects with nonmatching symmetry is challenging, but our electrostatic-based approach overcomes the symmetry mismatch by exploiting electrostatic interactions between oppositely charged cages. Moreover, our study showcases the use of nanoparticles as a contrast enhancer in an elegant way to gain insights into the structural details of crystalline biohybrid materials. The assembled materials were characterized with various methods, including transmission electron microscopy (TEM) and single-crystal small-angle X-ray diffraction (SC-SAXD). We employed cryo-plasma-focused ion beam milling (cryo-PFIB) to prepare lamellae for the investigation of nanoparticle sublattices via electron cryo-tomography. Importantly, we refined superlattice structure data obtained from single-crystal SAXD experiments, providing conclusive evidence of the final assembly type. Our findings highlight the versatility of protein nanocages for creating distinctive types of binary superlattices. Because the nanoparticles do not influence the type of assembly, protein cage matrices can combine various nanoparticles in the solid state. This study not only contributes to the expanding repertoire of nanoparticle assembly methods but also demonstrates the power of advanced characterization techniques in elucidating the structural intricacies of these biohybrid materials.

Conducting Polymer-Based Gel Materials: Synthesis, Morphology, Thermal Properties, and Applications in Supercapacitors.

Despite the numerous ongoing research studies in the area of conducting polymer-based electrode materials for supercapacitors, the implementation has been inadequate for commercialization. Further understanding is required for the design and synthesis of suitable materials like conducting polymer-based gels as electrode materials for supercapacitor applications. Among the polymers, conductive polymer gels (CPGs) have generated great curiosity for their use as supercapacitors, owing to their attractive qualities like integrated 3D porous nanostructures, softness features, very good conductivity, greater pseudo capacitance, and environmental friendliness. In this review, we describe the current progress on the synthesis of CPGs for supercapacitor applications along with their morphological behaviors and thermal properties. We clearly explain the synthesis approaches and related phenomena, including electrochemical approaches for supercapacitors, especially their potential applications as supercapacitors based on these materials. Focus is also given to the recent advances of CPG-based electrodes for supercapacitors, and the electrochemical performances of CP-based promising composites with CNT, graphene oxides, and metal oxides is discussed. This review may provide an extensive reference for forthcoming insights into CPG-based supercapacitors for large-scale applications.

Selective Synthesis and Crystal Chemistry of Candidate Rare-Earth Kitaev Materials: Honeycomb and Hyperhoneycomb Na2PrO3.

Rare-earth oxides have attracted interest as a platform for studying frustrated magnetism arising from bond-dependent anisotropic interactions. Ordered rock salt compounds Na2PrO3 crystallize in two polymorphs (α and β) comprising honeycomb and hyperhoneycomb lattices of octahedrally coordinated Pr4+ (4f1). Although possible realization of antiferromagnetic Kitaev interactions is anticipated for these phases on the basis of ab initio models, the air sensitivity of the two polymorphs has hampered reliable crystal growth and physical property measurements. Here, we have succeeded in preparing powder and single crystals of both α- and β-Na2PrO3 using modified synthetic procedures. Revised crystal structures for both polymorphs are obtained from refinement of untwinned single-crystal X-ray diffraction data.

Electrochemical Homo- and Crossannulation of Alkynes and Nitriles for the Regio- and Chemoselective Synthesis of 3,6-Diarylpyridines.

We disclose a mediated electrochemical [2+2+2] annulation of alkynes with nitriles, forming substituted pyridines in a single step from low-cost, readily available starting materials. The combination of electrochemistry and a triarylamine redox mediator obviates the requirements of transition metals and additional oxidants. Besides the formation of diarylpyridine moieties via the homocoupling of two identical alkynes, the heterocoupling of two different alkynes depending on their electronic nature is possible, highlighting the unprecedented control of chemoselectivity in this catalytic [2+2+2] process. Mechanistic investigations like cyclic voltammetry and crossover experiments combined with DFT calculations indicate the initial oxidation of an alkyne as the key step leading to the formation of a vinyl radical cation intermediate. The utilization of continuous flow technology proved instrumental for an efficient process scale-up. The utility of the products is exemplified by the synthesis of π-extended molecules, being relevant for material or drug synthesis.