The rising prospects of mechanochemically assisted syntheses hold promise for both academia and industry, yet they face challenges in understanding and, therefore, anticipating respective reaction kinetics. Particularly, dependencies based on variations in milling equipment remain little understood and globally overlooked. This study aims to address this issue by identifying critical parameters through kinematic models, facilitating the reproducibility of mechanochemical reactions across the most prominent mills in laboratory settings, namely planetary and mixer mills. Through a series of selected experiments replicating major classes of organic, organometallic, transition metal-catalyzed, and inorganic reactions from literature, we rationalize the independence of kinematic parameters on reaction kinetics when the accumulated energy criterion is met. As a step forward and to facilitate the practicability of our findings, we provide a freely accessible online tool† that allows the calculation of respective energy parameters for different planetary and mixer mills. Our work advances the current understanding of mechanochemistry and lays the foundation for future rational exploration in this rapidly evolving field.

Rechargeable magnesium batteries (rMBs) are promising candidates for next-generation batteries in which sulfides are widely used as cathode materials. The slow kinetics, low redox reversibility, and poor magnesium storage stability induced by the large Coulombic resistance and ionic polarization of Mg2+ ions have obstructed the development of high-performance rMBs. Herein, a Cu1.8S1-xSex cathode material with a two-dimensional sheet structure has been prepared by an anion-tuning strategy, achieving improved magnesium storage capacity and cycling stability. Element-specific synchrotron radiation analysis is evidence that selenium incorporation has indeed changed the chemical state of Cu species. Density functional theory calculations combined with kinetics analysis reveal that the anionic substitution endows the Cu1.8S1-xSex electrode with favorable charge-transfer kinetics and low ion diffusion barrier. The principal magnesium storage mechanisms and structural evolution process have been revealed in details based on a series of ex situ investigations. Our findings provide an effective heteroatom-tuning tactic of optimizing electrode structure toward advanced energy storage devices.

Two-dimensional transition metal carbides/nitrides (MXenes) have shown great promise in various applications. However, mass production of MXenes suffers from the excessive use of toxic fluorine-containing reagents. Herein, a new method was validated for synthesizing MXenes from five MAX ceramics. The method features a minimized (stoichiometric) dosage of F-containing reagent (NaBF4) and polyols (glycerol, erythritol, and xylitol) as the reaction solvent. Due to the sweetness of polyols and the low environmental impact, we refer to this method as a \"sweet\" synthesis of MXenes. An in-depth molecular dynamics simulation study, combined with experimental kinetic parameters, further revealed that the diffusion of F- in the confined interplanar space is rate-determining for the etching reaction. The expansion of interlayer spacing by polyols effectively reduces the diffusion activation energy of F- and accelerates the etching reaction.

5-methyl-2-hexanone is used as a versatile polymerization solvent for industrial preparation processes of bulk and fine chemicals. An efficient catalyst, Pd/γ-Al2O3, is reported for the preparation of 5-methyl-2-hexanone by selective hydrogenation of 5-methyl-3-hexen-2-one. The catalyst exhibits remarkable activity and selectivity even at atmospheric pressure and low temperature (1 atm, 80 °C). The influence weight of reaction conditions on the reaction process was obtained through the Artificial Neural Network model, which were reaction pressure, reaction temperature and liquid hourly space velocity in order. The reaction kinetics and mechanism of 5-methyl-2-hexanone preparation by hydrogenation over Pd/γ-Al2O3 catalyst were investigated. The hydrogenation reaction pathway of 5-methyl-3-hexen-2-one was obtained by using Density functional theory calculations, and the mechanism of selective hydrogenation of CC double bonds and CO double bonds was revealed. A kinetic model based on the LHHW model assumption was also proposed and compared with experimental results demonstrating good predictability.

The calcium looping technology employing CaO-based sorbents is pivotal for capturing CO2 from flue gas. However, the intrinsic low thermodynamic stability of CaO-based sorbents and the requisite molding step induce severe sintering issues, diminishing their cyclic stability. Herein, a high-entropy fluorite oxide (HEFO) inert stabilizer premised on entropy stabilization and synergistic effect strategies is introduced. HEFO-modified, CaO-based sorbent pellets are synthesized via a rapid cigarette butt-assisted combustion process (15 min) combined with the graphite molding method. Post-multiple cycles, their CO2 capture capacity reaches 0.373 g g-1, which is 2.6-fold superior to that of pure CaO, demonstrating markedly enhanced anti-sintering properties. First, the subtle morphological and crystallographic modifications suggest that the inherent entropy stability of HEFO imparts robust thermal resistance. Concurrently, the disordered structure of single-phase HEFO exhibits a high affinity for CaO, resulting in an interface binding energy of -1.83 eV, in sharp contrast to the -0.112 eV of pure CaO, thereby restricting CaO migration. Additionally, the multi-element synergistic effect of HEFO reduces the energy barrier by 0.15 eV, leading to a 40% and 140% increase in carbonation and calcination rates, respectively. This work presents highly efficient and rapidly synthesized CaO-based sorbent pellets, showcasing promising potential for industrial application.

Biological reproduction rests ultimately on chemical autocatalysis. Autocatalytic chemical cycles are thought to have played an important role in the chemical complexification en route to life. There are two, related issues: what chemical transformations allow such cycles to form, and at what speed they are operating. Here we investigate the latter question for solitary as well as competitive autocatalytic cycles in resource-unlimited batch and resource-limited chemostat systems. The speed of growth tends to decrease with the length of a cycle. Reversibility of the reproductive step results in parabolic growth that is conducive to competitive coexistence. Reversibility of resource uptake also slows down growth. Unilateral help by a cycle of its competitor tends to favour the competitor (in effect a parasite on the helper), rendering coexistence unlikely. We also show that deep learning is able to predict the outcome of competition just from the topology and the kinetic rate constants, provided the training set is large enough. These investigations pave the way for studying autocatalytic cycles with more complicated coupling, such as mutual catalysis.

Cannabinoid decarboxylation via thermo-chemical conversion has the potential to reduce the cannabinoid degradation and evaporation due to short reaction time and use of water as the solvent. When combined with pressurized liquid extraction (PLE), thermo-chemical conversion can be performed as the first stage in the extraction procedure. PLE utilizes a closed system at elevated temperatures and pressure to increase the solvation power, which contributes to decreased viscosity and increased diffusion rate. With this new in-extraction decarboxylation approach there remain variables that need full understanding before up scaling from bench top to pilot or commercial scale. Herein, the thermo-chemical decarboxylation kinetics was studied for industrial hemp via PLE at different temperatures (80-160 °C) and reaction times (1-90 min). The reaction was found to be pseudo-first order. Model verification on CBD and CBG resulted in acceptable results; however, an anomaly in the minor cannabinoids suggests that cannabinoid concentration may influence model kinetics.

Carbodiimides are important crosslinkers in organic synthesis and are used in the isocyanate industry as modifier additives. Therefore, the understanding of their formation is of high importance. In this work, we present a theoretical B3LYP/6-31G(d) and SMD solvent model and experimental investigation of the formation of diphenylcarbodiimide (CDI) from phenyl isocyanate using a phosphorus-based catalyst (MPPO) in ortho-dichlorobenzene (ODCB) solvent. Kinetic experiments were based on the volumetric quantitation of CO2 evolved, at different temperatures between 40 and 80 °C. Based on DFT calculations, we managed to construct a more detailed reaction mechanism compared to previous studies which is supported by experimental results. DFT calculations revealed that the mechanism is composed of two main parts, and the rate determining step of the first part, controlling the CO2 formation, is the first transition state with a 52.9 kJ mol-1 enthalpy barrier. The experimental activation energy was obtained from the Arrhenius plot (ln k vs. 1/T) using the observed second-order kinetics, and the obtained 55.8 ± 2.1 kJ mol-1 was in excellent agreement with the computational one, validating the complete mechanism, giving a better understanding of carbodiimide production from isocyanates.

OBJECTIVE: The gradients in surfactant distribution at a fluid-fluid interface can induce fluid flow known as the Marangoni flow. Fluid interfaces found in biological and environmental systems are seldom clean, where mixtures of various surfactants are present. The presence of multi-component surfactant mixtures introduces the possibility of interactions among constituents, which may impact Marangoni flows and alter flow dynamics.
METHODS: We employed flow visualization, surface tension and reaction kinetic measurements, and numerical simulations to quantitatively investigate the Marangoni flows induced by the reacting surfactant mixtures. Different binary surfactant mixtures were utilized for comparative analysis.
RESULTS: The impact of surfactant interactions on Marangoni flows is confirmed through the observation of diverse complex flow patterns that result from the combination of oppositely charged surfactants in varying composition ratios and concentrations. Unique flow patterns originate from the composition-dependent interfacial phenomena upon mixing surfactants. Our findings provide vital insights that could be used to guide the development of effective oil remediation or the spreading of waterborne pathogens in contaminated regions.

β-lactam antibiotics, extensively used worldwide, pose significant risks to human health and ecological safety due to their accumulation in the environment. Recent studies have demonstrated the efficacy of transition metal-activated sulfite systems, like Fe(Ⅲ)/HSO3-, in removing PPCPs from water. However, research on their capability to degrade β-lactam antibiotics remains sparse. This paper evaluates the degradation of 14 types of β-lactam antibiotics in Fe(Ⅲ)/HSO3- system and establishes a QSAR model correlating molecular descriptors with degradation rates using the MLR method. Using cefazolin as a case study, this research predicts degradation pathways through NPA charge and Fukui function analysis, corroborated by UPLC-MS product analysis. The investigation further explores the influence of variables such as HSO3- dosage, substrate concentration, Fe(Ⅲ) dosage, initial pH and the presence of common seen water matrices including humic acid and bicarbonate on the degradation efficiency. Optimal conditions for cefazolin degradation in Fe(Ⅲ)/HSO3- system were determined to be 93.3 μM HSO3-, 8.12 μM Fe(Ⅲ) and an initial pH of 3.61, under which the interaction of Fe(Ⅲ) dosage with initial pH was found to significantly affect the degradation efficiency. This study not only provides a novel degradation approach for β-lactam antibiotics but also expands the theoretical application horizon of the Fe(Ⅲ)/HSO3- system.