Reaction Of Precursor Research Articles

Flexible Coordination of SacNac Ligands in Iridium Complexes and their Application to Catalytic Hydroboration

AbstractHerein, we report the synthesis and characterization of a small family of Ir(I) and Ir(III) complexes supported by β‐thioketoiminates (SacNac) ligands. All complexes were fully characterized by IR, 1D and 2D NMR, and Elemental Analysis (e.a.) experiments. X‐ray diffraction studies were carried out to corroborate the structure of compounds [Ir(cod)(SacNac)] (1) (cod=1,5‐cyclooctadiene), [Ir(dmb)(SacNac)] (2) (dmb=2,3‐dimethyl‐1,3‐butadiene) and [IrCp*(SacNac‐H)(Cl)2] (8) (Cp*=pentamethyl‐cyclopentadienyl). Complexes 1 and 2 are Ir(I) species and have square‐planar geometry in solid state, with bond angles and distances that suggest semi‐aromaticity in the six‐membered ring. To the best of our knowledge, we report the first mono‐coordination mode of a SacNac ligand via sulfur atom in complex 8. Also, we report the first application of iridium‐SacNac complexes as catalytic precursors in hydroboration reactions, where Ir(III) species give the best results.

Atomically dispersed ruthenium single-atom alloy catalysts enabling efficient iodide oxidation reaction electrolysis in acidic media

Single-atom catalysts exhibit immense potential across diverse reactions, yet their synthesis and stability in acidic environments pose significant challenges. Herein, we introduce a facile one-step hydrothermal approach to fabricate Ru single-atom alloy catalysts (Ru SAAC) through the reaction of Ru and Ti precursors, followed by annealing in an argon atmosphere. Analysis via extended X-ray absorption fine structure spectroscopy and aberration-corrected scanning transmission electron microscopy confirms the atomically dispersed Ru alloy catalyst anchored on a TiO2 support. Remarkably, Ru SAAC demonstrates exceptional electrocatalytic performance in the iodide oxidation reaction (IOR), achieving a benchmark current density of 10 mA/cm2 at a mere voltage of 0.64 V in acidic conditions within a three-electrode electrolyzer setup. Surpassing nanoscale Ru/TiO2 and RuO2/TiO2 counterparts, Ru SAAC exhibits the highest voltage efficiency (84.4%), lowest Tafel slope (36 mV/dec), and lowest overpotential (100 mV) under identical experimental conditions. This method enables facile control over Ru morphology. It enhances the kinetics and thermodynamic favorability of Ru SAAC in acidic media, opening avenues for synthesizing diverse transition metal-based single-alloy catalysts for varied applications.

Controlled Growth of Two-Dimensional SnSe/SnS Core/Crown Heterostructures.

We present a novel, straightforward, and reproducible one-pot heating up technique to synthesize core/crown SnSe/SnS nanosheets by a careful adjustment of the sulfur and selenium precursor reactivity. Here, the SnSe nanosheets are prepared via a wet-chemical route using SnCl2 and selenium phosphines. By adding a highly reactive S-oleylamine complex during the growth of the SnSe sheets at 240 °C, SnS crowns were formed within the SnSe sheets. The number of SnS crowns can be tailored upon repeated addition of S-oleylamine. A combination of transmission electron microscopy, high-resolution transmission electron microscopy, atomic force microscopy, scanning transmission electron microscopy, and energy-dispersive X-ray spectroscopy proves the formation of highly crystalline core/crown structures.

Modular Synthesis of Monoanionic PN Ligands Leads to Unexpected Structural Diversity in Lanthanum Chemistry.

We report a new synthetic entry to a series of N-substituted anilidophosphine ligands (short HPNR, R = pTol (HPNTol), 3,5-dimethylphenyl (HPN3,5Me), 3,5-bis(trifluoromethyl)phenyl (HPN3,5CF3), 2-methoxyphenyl (HPNOMe), diisopropylphenyl (HPNDipp), and adamantyl (HPNAd)), allowing a detailed tuning of their steric (and electronic) properties. HPNR could be converted into their lithium salts LiPNR, which are effective precursors for salt metathesis reactions. The new ligands are used for the synthesis of an array of lanthanide complexes using LaCl3(THF)1.2 as a precursor. Depending on the steric bulk of the anilidophosphine ligand, either chloride-bridged dimers of the general formula [(PNR)2La(μ-Cl2)La(PNR)2] (R = pTol (3f), 3,5-dimethylphenyl (3d) and adamantyl (3a)) or mononuclear complexes of the general formula (PNR)2LaCl (R = diisopropylphenyl (3e)) are observed, if the complexation reaction is carried out in toluene. Contrary, if salt metathesis reactions are carried out in dimethoxyethane (DME) as a coordinating solvent, -ate complexes of the general formula [(PNR)2La(μ-Cl2)Li(DME)] (R = Adamantyl (4a) and R = 2-methoxyphenyl (4d)) or [Li(DME)3][(PNR)2LaCl2] (R = 3,5-bis(trifluoromethyl)phenyl (4b), R = pTol (4f) and R = 3,5-dimethylphenyl (4d)) are observed. All ligands and complexes have been thoroughly characterized by 1D and 2D NMR spectroscopy, IR, and X-ray crystallography. Finally, the steric demand of the new anilidophosphine ligands is evaluated using SambVca simulations.

Data-driven inverse mix design for sustainable alkali-activated materials

Alkali-activated materials (AAMs) are promising alternatives to ordinary Portland cement (OPC), but standardized mix design approaches are limited. This study introduces a machine learning-based framework for inverse mix design of AAMs, predicting optimal mixes based on target properties and sustainability. The model considers eight key factors, including precursor reactivity, activator properties, and liquid-to-binder ratio. It operates in four steps: (i) constructing forward prediction models, (ii) generating new mix designs, (iii) evaluating workability and strength, and (iv) filtering for performance and sustainability. Experiments validated the model, targeting fluidity >100% and compressive strengths of 40 MPa (A40) and 50 MPa (A50). The A40 and A50 mixes achieved fluidities of 147.7% and 170.0%, and 28-day compressive strengths of 41.5 and 57.5 MPa. Both had lower environmental impacts (GWP, AP, and EP) compared to OPC-based mortars. This framework enhances AAM design efficiency and sustainability for broader applications.

Breaking Barriers in Chalcogenide Perovskite Synthesis: A Generalized Framework for Fabrication of BaMS3 (M═Ti, Zr, Hf) Materials

AbstractChalcogenide perovskites have garnered increasing attention as stable, non‐toxic alternatives to lead halide perovskites. However, their conventional synthesis at high temperatures (>1000 °C) has hindered widespread adoption. Recent studies have developed low‐to‐moderate temperature synthesis methods (<600 °C) using reactive precursors, yet a comprehensive understanding of the pivotal factors affecting reproducibility and repeatability remains elusive. This study delineates the critical factors in the low‐temperature synthesis of BaMS3 (M═Zr, Hf, Ti) compounds and presents a generalized framework. Innovative approaches are developed for synthesizing BaMS3 compounds using this framework involving organometallics for solution deposition. The molecular precursor routes, employing metal acetylacetonates to generate soluble metal–sulfur bonded complexes and metal–organic compounds to produce soluble metal‐thiolate, metal‐isothiocyanate, and metal‐trithiocarbonate species, are demonstrated to yield carbon‐free BaMS3. These methods have achieved the most contiguous films of BaZrS3 and BaHfS3 using solution deposition to date. Furthermore, a hybrid solution processing method involving stacking sputter‐deposited Zr and solution‐deposited BaS layers is employed to synthesize a contiguous, oxygen‐free BaZrS3 film. The diffuse reflectance measurements indicate a direct bandgap of ≈ 1.85 eV for the BaZrS3 films and ≈ 2.1 eV for the BaHfS3 film under investigation.

Enhanced Fluorescence in Green ZnSeTe Quantum Dots Using Gradient Layer Technique

AbstractA novel method is presented for synthesizing green ZnSeTe quantum dots (QDs) that demonstrate high photoluminescence quantum yield (PLQY) and a narrow full width at half maximum (FWHM). In this synthesis, a gradient layer is created between the ZnSeTe core and the ZnSe inner shell by utilizing the different reactivities of precursors. This innovative approach aims to reduce lattice mismatch and minimize interfacial defects, thereby enhancing the fluorescence properties of ZnSeTe QDs. Using the gradient layer, green QDs are achieved with a FWHM of 36 nm and a PLQY of 90%, surpassing previous results. Detailed structural analyses confirmed a reduction in stacking faults and strain in the QDs with a gradient layer, leading to enhanced fluorescence properties. The QDs with a gradient layer are successfully integrated into the emissive layer of a quantum dot light–emitting diode device, demonstrating superior performance compared to QDs without the gradient layer.

CO oxidation on single Pt atom supported by two-dimensional ZnO monolayer: Reaction mechanism and precursor activation

CO oxidation is an effective solution for controlling CO emissions, and supported single-atom catalysts have shown excellent catalytic reactivity for chemical reactions. CO oxidation on a single Pt atom supported by a two-dimensional ZnO monolayer is investigated by combing ab initio molecular dynamics and density functional theory calculations. Seven reaction mechanisms are identified, including two new trimolecular Elie-Riedel mechanisms; six of them, except for the Mars-van Krevelen mechanism, have rate-limiting step energy barriers between 0.31 and 0.47 eV, which is lower than the experimental activation barrier of 0.81 eV on single Pt atoms supported by bulk ZnO, and is much lower than that of about 1.0 eV on Pt(111) surface. Furthermore, two preferred reaction mechanisms are discovered, an Eley-Rideal mechanism and a trimolecular Eley-Rideal mechanism, both of which have rate-limiting step energy barriers as low as 0.31 eV. Our results show that the more antibonding orbitals are filled in the reaction precursor, the higher its activation level. Activation of precursors plays an important role in CO oxidation and leads to different mechanisms. These results provide insights into the design of efficient single-atom catalysts supported by two-dimensional materials for the removal of CO pollutants.

Examining Metal Complexes Formed from New Schiff Base ‎Ligand ‎Derived from Benzene Carbaldehyde: Evaluation of Anti-‎biofilm and ‎Anti-bacterial Properties

One of the most difficult tasks in modern medical societies is the process of identifying a cure for many infectious diseases caused by drug-resistant microbes. Therefore, it has become necessary to discover new compounds that work in this regard. The currently prepared Schiff base, derived from thiazole, has a biological activity against bacteria and biofilms and its activity increases when it is associated with copper, zinc and platinum ions and forms metal complexes. This study highlights the synthesis and evaluation of novel biological compounds as inhibitors of bacterial growth and biofilms. A three newly complexes are resulting from the reaction of a new Schiff base ligand (LC) with metal ions (Zn, Cu, Pt). The new ligand (LC) was prepared from the reaction of precursor (P) and benzenecarbaldehyde. The prepared compounds were characterized by 1H&13CNMR, FTIR, UV-Vis, Magnetic susceptibility, CHNS and Molar conductivity. It was determined that the anti-bacterial activity of the newly synthesized Lc and (Cu-Lc) was mightily significant towards more antibiotic-resistant bacteria and had low (MIC) values. Like that, anti-biofilm inhibitory of the same compounds showed 100% of clinical isolates of P. aeruginosa and S. aureus in 16 and 32 mg/ml respectively, whereas (Zn-Lc) were inhibited 100% in 4 mg/ml. On the other hand (Pt-Lc) inhibited 100 % in 2 mg/ ml. Good yield was obtained from the synthesis of new compounds from the starting material. They can be potential candidates as inhibitors of bacteria and biofilms.

On-surface synthesis of porous graphene nanoribbons mediated by phenyl migration

Advancements in the on-surface synthesis of atomically precise graphene nanostructures are propelled by the introduction of innovative precursor designs and reaction types. Until now, the latter has been confined to cross-coupling and cyclization reactions that involve the cleavage of specific atoms or groups. In this article, we elucidate how the migration of phenyl substituents attached to graphene nanoribbons can be harnessed to generate arrays of [18]-annulene pores at the edges of the nanostructures. This sequential pathway is revealed through a comprehensive study employing bond-resolved scanning tunneling microscopy and ab-initio computational techniques. The yield of pore formation is maximized by anchoring the graphene nanoribbons at steps of vicinal surfaces, underscoring the potential of these substrates to guide reaction paths. Our study introduces a new reaction to the on-surface synthesis toolbox along with a sequential route, altogether enabling the extension of this strategy towards the formation of other porous nanostructures.

Green synthesis and characterization of titanium dioxide nanoparticles and their photocatalytic activity

In this study, we compared two low-temperature synthesis procedures for the large-scale production of titania nanoparticles (NPs). The first takes place in an aqueous medium with an acidic environment, by using a triblock polymer surfactant (Pluronic 123). The second involves a polycondensation reaction of alkoxide precursors at 70 °C in a water-in-oil (W/O) microemulsion with a volume ratio of 1:1, using cetylpyridinium bromide (CPB) as a cationic surfactant. The morphological and structural characterization of the samples was carried out through Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD). The photoactivity of the nanostructured titania was evaluated by measuring the photodegradation of Methylene Blue (MB). The solvent-free synthetic approach provided spherical titania nanoparticles mainly constituted by rutile crystallites with a very good synthetic yield. However, the photodegradation rate of MB for such titania nanoparticles ranges from 30 % to 40 %, after 1h under solar irradiation. Conversely, titania nanoparticles obtained through microemulsion synthesis show a photodegradation rate of more than 90 % comparable to titania P25. This high-yield synthesis leads to the formation of TiO2 nanoparticles characterized by small crystallite aggregates (rutile and anatase).

Mechanical and shrinkage properties of alkali-activated mortars with graphite tailings

To improve the problems of high CO2 emission generated by the preparation of silicate cement, large accumulation of solid waste, and depletion of natural sand resources, this paper investigates the effect of pozzolanic effect of graphite tailings (GT) on the mechanical properties, shrinkage properties and microstructure of alkali-activated mortar, and less research has been done on this related content. This paper partially replaced the natural sand with GT, and completely replaced the cement with fly ash and slag to prepare alkali-activated fly ash-slag (AAFS) mortar. The consequences of GT replacement rate on the mechanical and shrinkage characteristics of AAFS mortar were analyzed. In addition, X-ray diffraction (XRD), mercury-in-pressure (MIP), and nuclear magnetic resonance (29Si MAS NMR) were used to examine the hydration degree, pore structure, and hydration products of AAFS mortar. The results demonstrated when the Na2O content was 7 % and the activator modulus was 1.0, the test group's 28-day flexural and compressive strengths at a 20 % GT replacement rate were increased by 19.49 % and 14.45 %, respectively, compared to the test group without GT. The appropriate quantity of GT reduced the AAFS mortar's drying shrinkage and increased the AAFS mortar's self-shrinkage. According to the microstructure analysis, GT had a pozzolanic effect: moderate doping of GT promoted the hydration reaction of precursors, improved the amount of C-(A)-S-H gel product generated, and improved AAFS mortar's mechanical and shrinkage properties.

Pathway and Production Differences in Branched-Chain Hydroxy Acids as Bioactive Metabolites in Limosilactobacillus fermentum, Ligilactobacillus salivarius, and Latilactobacillus sakei.

Branched-chain hydroxy acids (BCHAs) as bioactive metabolites of Lactobacillaceae include 2-hydroxy isovaleric acid (HIVA), 2-hydroxy isocaproic acid (HICA), and 2-hydroxy-3-methyl isovaleric acid (HMVA). Combining targeted and untargeted metabolomics, this study elucidates differences in extracellular BCHA production in Limosilactobacillus fermentum, Ligilactobacillus salivarius, and Latilactobacillus sakei alongside comparing comprehensive metabolic changes. Through targeted metabolomics, BCHA production among 38 strains exhibited strain specificity, except for L. sakei, which showed significantly lower BCHA production. Explaining the lower production in L. sakei, which lacks the branched-chain amino acid (BCAA)-utilizing pathway, comparison of BCHA production by precursor reaction revealed that the pathway utilizing BCAAs is more dominant than the pathway utilizing pyruvate. Expanding upon the targeted approach, untargeted metabolomics revealed the effects of the reaction compound on other metabolic pathways besides BCHAs. Metabolism alterations induced by BCAA reactions varied among species. Significant differences were observed in glycine, serine, and threonine metabolism, pyruvate metabolism, butanoate metabolism, and galactose metabolism (p < 0.05). These results emphasize the importance of the synergy between fermentation strains and substrates in influencing nutritional components of fermented foods. By uncovering novel aspects of BCAA metabolism pathways, this study could inform the selection of fermentation strains and support the targeted production of BCHAs.

Why Colloidal Syntheses of Bimetallic Nanoparticles Cannot be Generalized.

Introducing one general synthesis to form bimetallic nanoparticles (NPs) could accelerate the discovery of NPs for promising energy applications. Although colloidal syntheses can provide precise structural and morphological control of bimetallic NPs, the complex chemical nature of multicomponent syntheses challenges the realization of such synthetic simplicity. Common synthetic issues are frequently ascribed to the variation in metal ion precursor reactivities and complex chemical interactions between the different metal surfaces and capping agents employed. However, no systematic studies have shown how these factors compete to ultimately assign the factor limiting the mixing and formation of bimetallic NPs. Here, we provide a parametric investigation of how the intrinsic standard reduction potentials (E0red) of the metal ions and cocapping agents influence the formation of bimetallic AuCu, AuPd, and PdCu NPs. Using a combination of in situ X-ray total scattering along with transmission electron microscopy and nuclear magnetic resonance spectroscopy, we illustrate the multifunctional role of the cocapping agents through interactions with both the metal ion precursors and NP surfaces to stabilize metastable structures. Additionally, we demonstrate how system-specific side reactions and the local metal ion coordination environment can be used to selectively tune the formation kinetics, structure, and morphology of bimetallic NPs. Ultimately, these insights show that the chemical interactions rather than the intrinsic E0red are responsible for the formation of bimetallic NPs. Broadly, these insights should aid the synthetic design of tailored multimetallic NPs.

Review on the Polymeric and Chelate Gel Precursor for Li-Ion Battery Cathode Material Synthesis.

The rapid design of advanced materials depends on synthesis parameters and design. A wide range of materials can be synthesized using precursor reactions based on chelated gel and organic polymeric gel pathways. The desire to develop high-performance lithium-ion rechargeable batteries has motivated decades of research on the synthesis of battery active material particles with precise control of composition, phase-purity, and morphology. Among the most common methods reported in the literature to prepare precursors for lithium-ion battery active materials, sol-gel is characterized by simplicity, homogeneous mixing, and tuning of the particle shape. The chelate gel and organic polymeric gel precursor-based sol-gel method is efficient to promote desirable reaction conditions. Both precursor routes are commonly used to synthesize lithium-ion battery cathode active materials from raw materials such as inorganic salts in aqueous solutions or organic solvents. The purpose of this review is to discuss synthesis procedure and summarize the progress that has been made in producing crystalline particles of tunable and complex morphologies by sol-gel synthesis that can be used as active materials for lithium-ion batteries.

Exploring Gas‐Solid Phase Diagrams: Novel Methods for Oxyfluorination of Mn3O4 and Mn2O3 with Molecular Fluorine

AbstractFluorinated, manganese‐redox cation‐disordered rocksalts are promising candidates for high‐performance cobalt‐free Li‐ion cathode active material. A need for reactive fluorinated precursors was however identified. While manganese oxyfluorides are promising precursor candidates, none stable at room temperature was reported prior to 2023. The key to their recent synthesis by reacting molecular fluorine with MnO was a procedure to continuously scan the temperature axis in search of activation temperatures. In line with this philosophy of continuous exploration of the chemical space, two experimental procedures are reported to scan the stoichiometry axis of a gas‐solid phase diagram in search of transitions and intermediate compounds. Their application to F2 ‐ Mn3O4 and F2 ‐ Mn2O3 phase diagrams resulted in the discovery of two new ranges of stable manganese oxyfluorides of respective compositions MnO1.33‐0.13xFx with x&lt;0.5 and MnO1.5‐0.22xFx with x&lt;1.

Room Temperature Synthesis of Tellurium by Solution Atomic Layer Deposition.

This study demonstrates the deposition of tellurium (Te) on silicon/silicon nitride substrates using solution atomic layer deposition (sALD) at ambient temperature. The process employs tellurium tetrachloride (TeCl4) and bis(triethylsilyl)-telluride ((TES)2Te) as precursors, with toluene as the solvent. Growth parameters were optimized through systematic variation of the pulse and purge times. Morphological characterization via scanning and transmission electron microscopy revealed needle-like crystallites, while X-ray diffractometry confirmed the crystalline nature of the deposited Te. Increasing the number of deposition cycles resulted in larger Te crystallites and enhanced substrate surface coverage. A thin amorphous carbon shell surrounding the crystallites and carbon inclusions was observed, likely originating from the organic solvent. X-ray photoemission spectroscopy analysis indicated high-purity Te films with minimal surface oxidation. The small chlorine signal suggested a near-complete precursor reaction and the efficient purging of byproducts. This novel sALD approach presents a promising method for depositing Te on various surfaces under mild conditions.

Interlayer synergistic reaction of radical precursors for ultraefficient 1O2 generation via quinone-based covalent organic framework

Singlet oxygen (1O2) is important in the environmental remediation field, however, its efficient production has been severely hindered by the ultrafast self-quenching of the as-generated radical precursors in the Fenton-like reactions. Herein, we elaborately designed lamellar anthraquinone-based covalent organic frameworks (DAQ-COF) with sequential localization of the active sites (C═O) at molecular levels for visible-light-assisted peroxymonosulfate (PMS) activation. Theoretical and experimental results revealed that the radical precursors (SO5·-) were formed in the nearby layers with the migration distance less than 0.34 nm, via PMS donating electrons to the photogenerated holes. This interlayer synergistic effect eventually led to ultraefficient 1O2 production (14.8 μM s-1), which is 12 times that of the highest reported catalyst. As an outcome, DAQ-COF enabled the complete degradation of bisphenol A in 5 min with PMS under natural sunlight irradiation. This interlayer synergistic concept represents an innovative and effective strategy to increase the utilization efficiency of ultrashort-lived radical precursors, providing inspirations for subtle structural construction of Fenton-like catalysts.

Effect of Ga/Al ratio on the luminescent properties of inorganic scintillating GGAG:(4 mol%)Ce ceramic powder

Gadolinium gallium aluminum garnet doped with cerium (GGAG:Ce), a promising ceramic scintillator material, is being excessively explored for its high quality optical properties by the bandgap engineering with different Ga/Al ratio. In this study, GGAG:Ce powders were synthesized using a solvothermal method and sintered at 1300 °C to investigate the impact of the gallium-to-aluminum (Ga/Al) ratio on optical characteristics. The results revealed that a decrease in the Ga/Al ratio led to a decrease in particle size. This observation can be attributed to the different reactivity and growth kinetics of gallium and aluminum precursors during the solvothermal process. Perturbations from the optimized Ga/Al ratio of 1.5–1.77 and 1.27 resulted in substantially enhanced photoluminescence (PL) and radioluminescence (RL) spectra intensities. PL lifetime measurements of various Ga/Al ratio exhibit average PL lifetime between 48 and 57 ns. Specifically, the deviations to 1.77 and 1.27 ratios yielded approximately 125 % and 106 %, respectively, in observed luminescent measurements compared to other ratios. This enhancement in PL and RL intensity suggests that the Ga/Al ratio plays a critical role in modulating the optical properties of GGAG:Ce ceramic powders. The results of this study also highlight the importance of the Ga/Al ratio in tailoring the optical or luminescence characteristics of GGAG:Ce powders.

N-Difluoroacetylhexosamine as a Substrate-Engineering Precursor for Glycosylation Reactions.

We present the application of N-difluoroacetylglucosamine (GlcNDFA) in a chemical evolution strategy to synthesize oligosaccharides. In comparison to conventional N-trifluoroacetylglucosamine, GlcNDFA exhibits superior substrate compatibility with glycosyltransferases as well as stability in aqueous environments. Using our 16-step assembly line, GlcNDFA can be used to produce homogeneous dekaparin, a heparin-like medication, with a yield of 62.2%. This underscores the significant potential of GlcNDFA as a chemical evolution precursor in the precise synthesis of structurally defined polysaccharides.