Liquid Reaction Research Articles

Melt growth of crystalline α-SrSi2 by the vertical Bridgman method and its thermoelectric characteristics

As a candidate thermoelectric material operating in the low-temperature regime (room temperature to 473 K), we have examined α-SrSi2: a narrow bandgap semiconductor material, which is composed of environmentally benign elements. We are able to report the successful production of single-crystalline-like α-SrSi2 with clear semiconducting properties by melting synthesis, a thermodynamically stable and thermally equilibrium process that reduces unexpected process contamination and improves crystallinity.The crystals up to 20 × 20 × 5 mm3 have been obtained for a solid–liquid phase reaction temperature of 1308 K for 10 h with a growth rate averaging at 0.617 K/h in the temperature range from 1403 K to 1373 K. The band gap of this material was measured at 48 meV, which is higher than the values previously reported. The power factor was measured at 2.9 mW/mK2 at 300 K, which is the highest value ever reported for undoped α-SrSi2.Based on the experimental bandgap values, the hybrid functional was used to correct the first-principles calculation method, and the Seebeck coefficient obtained from the first-principles calculation was compared with experimental values. Which values showed good agreement with experimental values.

Discovery of Molecular Intermediates and Nonclassical Nanoparticle Formation Mechanisms by Liquid Phase Electron Microscopy and Reaction Throughput Analysis

Formation kinetics of metal nanoparticles are generally described via mass transport and thermodynamics‐based models, such as diffusion‐limited growth and classical nucleation theory (CNT). However, metal monomers are commonly assumed as precursors, leaving the identity of molecular intermediates and their contribution to nanoparticle formation unclear. Herein, liquid phase transmission electron microscopy (LPTEM) and reaction kinetic modeling are utilized to establish the nucleation and growth mechanisms and discover molecular intermediates during silver nanoparticle formation. Quantitative LPTEM measurements show that their nucleation rate decreases while growth rate is nearly invariant with electron dose rate. Reaction kinetic simulations show that Ag4 and Ag− follow a statistically similar dose rate dependence as the experimentally determined growth rate. We show that experimental growth rates are consistent with diffusion‐limited growth via the attachment of these species to nanoparticles. The dose rate dependence of nucleation rate is inconsistent with CNT. A reaction‐limited nucleation mechanism is proposed and it is demonstrated that experimental nucleation kinetics are consistent with Ag42+ aggregation rates at millisecond time scales. Reaction throughput analysis of the kinetic simulations uncovered formation and decay pathways mediating intermediate concentrations. We demonstrate the power of quantitative LPTEM combined with kinetic modeling for establishing nanoparticle formation mechanisms and principal intermediates.

On the"Staple" Effect in the d-Glucose Acetylation by Choline-Chloride Ethylene Glycol and Choline-Chloride Urea Deep Eutectic Solvents.

This work employs hybrid quantum mechanics molecular mechanics simulations coupled with an umbrella sampling technique to investigate the acetylation of d-glucose with acetic anhydride in two deep eutectic solvents (DESs): choline-chloride ethylene glycol (ChCl/Etg) and choline-chloride urea (ChCl/U). The reaction proceeds spontaneously, with activation free energy barriers of 18.19 ± 0.15 and 19.83 ± 0.15 kcal/mol for ChCl/Etg and ChCl/U, respectively. These values align with literature data for similar reactions in ionic liquids, highlighting the potential of DESs as green reaction media for wood modifications, while minimizing lignocellulosic matrix degradation. Energy pair distribution analysis, radial distribution functions, and noncovalent interactions reveal a more solvated transition state compared to the initial reactant state within ChCl/Etg, facilitating the acetylation reaction. Interestingly, combined distribution function analysis unveils a "staple" effect in both solvents, potentially hindering efficient product separation. The work further explores hydrogen bond networks and Kamlet-Taft solvatochromic parameters to elucidate the role of solvents in the reaction mechanism. It was observed that a notable decrease in activation energy is accompanied by increasing net basicity, along with a reduction in the "staple" effect. This suggests that solvent parameters could serve as an effective screening tool for identifying novel and efficient DESs for wood modifications.

Discovering Nanoparticle Formation Mechanisms and Molecular Intermediates with Liquid Phase Electron Microscopy and Reaction Networks

Discovering Nanoparticle Formation Mechanisms and Molecular Intermediates with Liquid Phase Electron Microscopy and Reaction Networks

The effect of swirling shear blade on gas-liquid flow pattern and mass transfer performance in Venturi injector

To address the challenge of low mass transfer efficiency of gas-liquid reaction in traditional reactors, this study proposes a new method to improve the gas-liquid mass transfer efficiency by integrating swirl shear blades (SSB) into Venturi injectors. The gas-liquid flow patterns in the mixing and diffusion sections between the Swirl Venturi Injector (SVI) and the Traditional Venturi Injector (TVI) was compared, and it was found that the SSB significantly reduced the proportion of annular flow while increased the proportion of mist flow. The enhancement factor αE and the acceleration factor αA are applied to evaluate the mass transfer performance. Compared to TVI, the maximum αA of SVI was 29%, and the maximum αE was 43%. This work shows great potential in efficiently capturing gas components with low solubility in the liquid phase, thereby helping to achieve the goal of green chemical engineering.

A Reverse Thinking Based on Partially Methylated Aldononitrile Acetates to Analyze Glycoside Linkages of Polysaccharides Using Liquid Chromatography-Multiple Reaction Monitoring Mass Spectrometry.

Glycoside linkage analyses of medicine and food homologous plant polysaccharides have always been a key point and a difficulty of structural characterization. The gas chromatography-mass spectrometry (GC-MS) method is one of the commonly used traditional techniques to determine glycoside linkages via partially methylated alditol acetates and aldononitrile acetates (PMAAs and PMANs). Due to the simplicity of derivatization and the highly structural asymmetry of PMANs, reverse thinking is proposed using liquid chromatography-electrospray ionization-multiple reaction monitoring mass spectrometry (LC-ESI-MRM-MS) for the first time to directly determine the neutral and acidic glycosyl linkages of polysaccharides. The complete characterization of glycoside linkages deduced from PMANs was achieved using a combination of tR values, characteristic MRM ion pairs, diagnostic ESI+-MS/MS fragmentation ions (DFIs), and optimal collision energy (OCE). The DFI and OCE parameters were confirmed to be effective for the auxiliary discrimination of some isomers of the PMANs. The practicality of LC-ESI+-MRM-MS was further verified by analyzing the glycoside linkages of polysaccharides in five medicine and food homologous plants. This method can serve as an alternative to GC-MS for the simultaneous determination of neutral and acidic glycosyl linkages in polysaccharides.

Kinetically Controlled Self-Assembly of Ag Nanoclusters with Enhanced Luminescence.

Constructing self-assembly with definite assembly structure-property correlation is of great significance for expanding the property richness and functional diversity of metal nanoclusters (NCs). Herein, a well-designed liquid reaction strategy was developed through which a highly ordered nanofiber superstructure with enhanced green photoluminescence (PL) was obtained via self-assembly of the individual silver nanoclusters (Ag NCs). By visual monitoring of the kinetic reaction process using time-dependent and in situ spectroscopy measurements, the assembling structure growth and the structure-determined luminescence mechanisms were revealed. The as-prepared nanofibers featured a series of advantages involving a high emission efficiency, large Stokes shift, homogeneous chromophore, excellent photostability, high temperature, and pH sensibility. By virtue of these merits, they were successfully employed in various fields of luminescent inks, encryption and anticounterfeiting platforms, and optoelectronic light-emitting diode (LED) devices.

Low-Temperature Catalytic Transfer Hydrogenation of Biomass-Derived Furfural over Irreversibly Adsorbed and Highly Dispersed Zr(IV) Species.

Developing pure inorganic catalysts for low-energy transfer hydrogenation of biomass-derived furfural and alcohols below 100 °C is still challenging. This work reports highly dispersed Zr(IV) species catalysts prepared by irreversible adsorption of different solvent-dissolved Zr(IV) cations such as Zr4+ or [Zr4(OH)8(H2O)16]8+ on/in SBA-15 through Zr-O coordination, without adding an alkaline precipitant and calcination treatment. In the transfer hydrogenation of furfural to furfuryl alcohol, the Zr(IV) species catalysts exhibited unexpectedly outstanding transfer hydrogenation activity at low temperatures of 70 and 85 °C, superior to other transition-metal (Zr4+, Hf4+, Fe3+, etc.)- and main-group metal (Al3+, etc.)-based inorganic catalysts, which need high reaction temperatures above 100 °C, and comparable to the best-performing metal-organic hybrid catalysts with precise defect engineering modification or specific macromolecular ligands, and had negligible Zr leaching amounts (<0.01%) in water and in the collected liquid reaction medium from 7 cycles of reactions. In addition, the large strong Lewis acidic site amount rather than the large total acidic amount is a crucial condition for the catalysts to obtain high transfer hydrogenation activity, and basic sites were also involved in catalysis, and their absence would induce the acetalization side reaction. Furthermore, the catalysts were universal for low-temperature transfer hydrogenation of other aldehydes.

Hydrothermal Dissolution of Reactive Silica Materials in Sodium Hydroxide Lyes

AbstractReactive silica materials like vitreous silica or cristobalite were dissolved at temperatures between 100 and 220 °C for up to 7 days in NaOH lyes. The liquid and solid reaction products were analyzed chemically. Sodium water glasses with silica concentrations of up to 27 wt % and molar SiO2/Na2O ratios of up to 3.7 were obtained. The experimental data were evaluated by an approximation algorithm. The initial size reduction rates ranged between 0.1 and 7 µm h−1, depending on the temperature and the choice of starting materials. Correlations between thermodynamics and kinetics were discussed.

The denitrification characteristics of Na2S2O8 solution in a falling film reactor

ABSTRACT Wet scrubbing technology is an effective emission control technology for marine diesel engines. Nitric oxide (NO) is one of the main component of ship emissions, the sodium persulfate (Na2S2O8) can facilitate the NO mass transfer process to a rapid reaction. Falling film reactors are widely used in rapid gas–liquid reactions, however, the reaction characteristics of denitrification using Na2S2O8 solution in a falling film reactor are not clear, which were investigated in this paper. The factors of NO mass transfer flux were tested with the liquid–gas ratio of 15 L/m3. The effects of solution properties and temperatures on the reaction driving force were studied by calculating the chemical reaction equilibrium constants and Gibbs free energy changes. The results showed that the NO mass transfer flux increased with the increase of temperature, Na2S2O8 concentration, O2 concentration and NO concentration. NO mass transfer flux increased by 41.00% and then decreased by 2.12% as the pH value increased from 7 to 10 and then rising to 12. The Gibbs free energy changes of alkaline solutions were 114.22%−130.99% lower than those of acidic solution at 303–343 K, and the chemical reaction equilibrium constants were higher. Na2S2O8/seawater system has great application potential in marine exhaust gas purification.

Absorption in a pseudo-first-order regime with two irreversible reactions: Influence of the second reaction on the transfer rate

Gas-absorbing liquids such as CO2 often undergo two reactions: a main reaction and a secondary reaction. The solute flux transferred is a result of both reactions. Kinetics is one of the most important properties in the design of an absorber. To access the rate constant of the main reaction, the assumption of a pseudo-first-order (PFO) regime is often made, but the criteria for the system to be in a pseudo-first-order regime change between researchers. Furthermore, the impact of the secondary reaction is either neglected or overestimated. Recently, some researchers carried out simulations of multiple parallel gas–liquid reactions in the instantaneous regime and developed generalized criteria for this regime. In this study, to estimate the impact of the secondary reaction in a PFO regime, hundreds of simulations were carried out with two irreversible reactions within the framework of the film theory. This work proves that for Ha1 > 10, Ha2 > 10, Ha1/E∞,1 < 0.5, Ha2/E∞,2 < 0.5, normalized concentration profiles depend only on three factors: Ha1/ E∞,1, Ha2/ E∞,2, and Ha1/Ha2. Curves and generalized equations are provided enabling the estimation of the concentrations of reactants at the interface, the enhancement factor, and the influence of each reaction on the gas transfer flux (average absolute relative deviation ≤ 0.50 %). New criteria for determining whether the system can be considered in a pseudo-first-order regime are defined, giving accurate predictions with a success rate of 96.2 %.

Stable SnAgCu solder joints reinforced by nickel-coated carbon fiber for electronic packaging

Today’s 3D electronic packaging is characterized by smaller size and higher functional density, which generally require multiple reflow cycles. However, due to the Ostwald ripening process of the interfacial intermetallic compound (IMC), the solder joint’s strength would decrease as the number of reflow cycles increases. To address this, we developed a novel composite solder by incorporating nickel-coated carbon fiber (Ni@CF) into the Sn–3.0Ag–0.5Cu (SAC305) solder connection. The study showed that Ni@CF effectively enhanced the stability and reliability of solder joints during multiple reflow processes. Compared with Ni@CF-free equivalents, Ni@CFs promoted the nucleation of interfacial IMC during the solid–liquid reaction and inhibited Ostwald ripening, leading to a refinement of the interfacial IMC grains. As a result, the interface was strengthened, and the shift of shear fracture to the brittle interface seen in the SAC305 solder joint with multiple reflows did not occur in the composite solder joint. Furthermore, carbon fiber strengthened the solder matrix through the load transfer and shear-off mechanisms, depending on its inclination angle with the shear plane. Consequently, the Ni@CFs-reinforced solder joints maintained a shear strength of over 42 MPa throughout ten reflow cycles, while the pristine SAC305 solder joint exhibited decreased shear strength to 33 MPa. This study provides new insights into composite solder joints’ stability and reinforcement characteristics when subjected to multiple reflows.

Synthesis, structure and photoluminescent properties of far-red Y3Ga5O12:Cr3+ phosphors

Far-red (FR) photosensitive pigment (PFR) is vital for plant photomorphogenesis. Phosphor-converted (pc) LEDs are the next-generation FR light devices. How to obtain FR-emitting phosphors with a good quantum efficiency, suitable photoluminescence and high thermal stability is still difficult. Herein, we optimize the Y3Ga5O12:Cr3+ FR phosphor, which has an emission peak at 711 nm and a full width at half maximum of 74 nm, closing to the PFR absorption band. By adopting the solid-state sintering technology, the internal quantum efficiency reaches 85.5 %, more than 1.5 times higher than that reported by the liquid reaction (55 %). Furthermore, the external quantum efficiency reaches as high as 33.1 %, indicating the promising application in FR-LEDs.

Sample-in-answer-out centrifugal microfluidic chip reaction biosensor powered by Thermus thermophilus Argonaute (TtAgo) for rapid, highly sensitive and multiplexed molecular diagnostics of foodborne bacterial pathogens

Foodborne pathogens endanger public health and rapid, sensitive and accurate detection of them is vital. Argonaute stands in the frontline as the next generation nucleic acid detection tool, bearing a few comparable advantages. Centrifugal microfluidic chips (CMCs) use centrifugal force to achieve liquid flowing, mixing and reaction, eliminating complicated designs of valves and pumps. In this study, for the first time, we devised a Thermus thermophilusArgonaute (TtAgo)-powered centrifugal microfluidic chip reaction biosensor for Sample-in-Answer-out detection of Pathogen S. aureus (termed as ASAP) with ultrahigh rapidity and sensitivity in a one-pot fashion. The samples subjected to testing were mixed with a home-made nucleic acid fast extraction reagent and then the mixture was injected into the sample cell of CMC, which was centrifuged down into the reaction cell. The reaction cell was preloaded with both LAMP (Loop-mediated isothermal amplification) and TtAgo systems. As such, the species-specific nuc genes were amplified by LAMP, while the TtAgo performed site-specific cleavage to output fluorescent (FL) signals. The sample-to-answer time was 17 min, and the limit of detection (LOD) reached 1 CFU/mL. ASAP was able to perform simultaneous multiplexed detection and up to 16 samples can be detected at the same time. ASAP reduced reagent consumption and minimized the influence of carry-over and cross-contamination. ASAP was capable of detecting S. aureus in foods, but also detecting physiological samples from infect, holding great promise for practical applications. Overall, our work has enriched the Argonaute-powered biosensing and CMC biosensor technology by providing a conceptually novel bacterial detection platform.

Colloidal formation process based on electrophoretic phenomena of charged particles in liquid media and electrode reactions

Colloidal formation process based on electrophoretic phenomena of charged particles in liquid media and electrode reactions

NOx Prediction of Supersonic Coherent Jets for Electric Arc Steelmaking Furnace

Supersonic coherent jets are widely in practice in steelmaking processes including electric arc furnaces (EAF). Injecting oxygen through such coherent jets plays a vital role in enhancing the liquid gas mixing and reaction rates leading to boosting energy efficiency. Several experiments and numerical simulations have been carried out to understand the physical phenomenon of the coherent jets and to predict the behavior of the jets. However, the research on pollutant formation in the coherent jets for steelmaking is limited. As the industry transitions toward reducing emissions, prediction of pollutant formation is crucial. This numerical study analyzes both methane shrouding coherent jets and hydrogen shrouding coherent jets and predicts the NOx (oxides of nitrogen) formation. It has been found that NO concentration dominates over N2O and NO2 and has the highest concentration around the jet. Although the NO concentration reaches as high as 1070 ppm at high-temperature region around the jet, it remains below 225 ppm along the fuel inlet axis. Also, it has found that the NOx concentrations increase along the radial direction up to 1.5De\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$1.5{\ ext{De}}$$\\end{document} from the jet central line and gradually decreases, whereas the NO concentration peaks at 15De\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$15{\ ext{D}}_{{\ ext{e}}}$$\\end{document} along the jet axis in the downstream direction.

Development of Dry and Liquid Duplex Reagent Mix-Based Polymerase Chain Reaction Assays as Novel Tools for the Rapid and Easy Quantification of Bovine Leukemia Virus (BLV) Proviral Loads.

Bovine leukemia virus (BLV) is prevalent worldwide, causing serious problems in the cattle industry. The BLV proviral load (PVL) is a useful index for estimating disease progression and transmission risk. We previously developed a quantitative real-time PCR (qPCR) assay to measure the PVL using the coordination of common motif (CoCoMo) degenerate primers. Here, we constructed a novel duplex BLV-CoCoMo qPCR assay that can amplify two genes simultaneously using a FAM-labeled MGB probe for the BLV LTR gene and a VIC-labeled MGB probe for the BoLA-DRA gene. This liquid duplex assay maintained its original sensitivity and reproducibility in field samples. Furthermore, we developed a dry duplex assay composed of PCR reagents necessary for the optimized liquid duplex assay. We observed a strong positive correlation between the PVLs measured using the dry and liquid duplex assays. Validation analyses showed that the sensitivity of the dry duplex assay was slightly lower than that of the other methods for the detection of a BLV molecular clone, but it showed similar sensitivity to the singleplex assay and slightly higher sensitivity than the liquid duplex assay for the PVL quantification of 82 field samples. Thus, our liquid and dry duplex assays are useful for measuring the BLV PVL in field samples, similar to the original singleplex assay.

Unveiling the pathways of ethanol decomposition to carbon radicals by nanosecond pulse bubble discharge in liquid: a two-step hybrid model

In recent years, bubble discharge in liquid has become a novel approach for the synthesis of carbon nanomaterials; however, the fundamental discharge process and synthesis mechanism are still not well understood. In this work, we build a two-step simulation model (combining 2D fluid dynamics and zero-dimensional plasma kinetics) to investigate nanosecond pulse discharge in an Ar bubble immersed in liquid ethanol and chemical reaction processes inside. The 2D simulation results show that discharge develops along the gas‒liquid interface where ethanol decomposes, resulting in much higher densities of active species (CH3, C2H5 and OH). The electric field of the selected reference point near the interface obtained by the 2D model is transmitted into the 0D model. The numerical results show that the decomposition of ethanol mainly occurs at the discharge stage, in which electron impact dissociation (e.g. C2H5OH + e → CH2OH + CH3 + e) and Penning dissociation (e.g. C2H5OH + Ar* → CH2OH + CH3 + Ar) dominate. The density of all carbonaceous species rapidly increases during discharge, while that of some carbon radicals (CH and C) continues to increase due to neutral species reactions when discharge ceases. By quantitative analysis of the reaction contributions, the dominant pathways of C2, CH and C are revealed, i.e. C2H5OH → C2H5 → [C2H, C2H2, C2H3] → C2 and C2H5OH → CH3 → CH2 → CH → C. In addition, the formation pathways of H and OH radicals, which are indispensable for the transformation of carbonaceous intermediates, are also analysed.

Laser synthesis of nanoparticles in organic solvents - products, reactions, and perspectives.

Laser synthesis and processing of colloids (LSPC) is an established method for producing functional and durable nanomaterials and catalysts in virtually any liquid of choice. While the redox reactions during laser synthesis in water are fairly well understood, the corresponding reactions in organic liquids remain elusive, particularly because of the much greater complexity of carbon chemistry. To this end, this article first reviews the knowledge base of chemical reactions during LSPC and then deduces identifiable reaction pathways and mechanisms. This review also includes findings that are specific to the LSPC method variants laser ablation (LAL), fragmentation (LFL), melting (LML), and reduction (LRL) in organic liquids. A particular focus will be set on permanent gases, liquid hydrocarbons, and solid, carbonaceous species generated, including the formation of doped, compounded, and encapsulated nanoparticles. It will be shown how the choice of solvent, synthesis method, and laser parameters influence the nanostructure formation as well as the amount and chain length of the generated polyyne by-products. Finally, theoretical approaches to address the mechanisms of organic liquid decomposition and carbon shell formation are highlighted and discussed regarding current challenges and future perspectives of LSPC using organic liquids instead of water.

Synthesis of chiral phosphine-functionalized ionic liquids and their application in asymmetric hydrogenation

Abstract The present report prepared three novel chiral phosphine-functionalized polyetherimidazolium ionic liquids through ion-exchange reactions of chiral sulfonated BINAP ligands and hydroxyl-functionalized polyetherimidazolium ionic liquids grounded on the phosphine ligand-ionic liquid integration. Using these synthetics, methyl acetoacetate was subjected to asymmetric homogeneous hydrogenation catalyzed by ruthenium. The structural characterization of the three chiral phosphine-functionalized polyetherimidazolium ionic liquids was conducted using 1H NMR, 13C NMR, and 31P NMR in combination with HR-MS. Compared with their precursor sulfonated BINAP, the prepared chiral phosphine-functionalized ionic liquids exhibited comparable or better catalytic activity and enantioselectivity.