Kinetic Energy Dose as a Unified Metric for Comparing Ball Mills in the Mechanocatalytic Depolymerization of Lignocellulose

Mechanochemistry utilizes mechanical forces to activate chemical bonds. It offers environmentally benign routes for both (bio) organic and inorganic syntheses. However, direct comparison of mechanochemistry results is often very challenging. In mechanochemical synthetic protocols, ball mill setup (mechanical design and grinding vessel geometry) in addition to experimental parameters (milling frequency, duration, ball count and size) vary broadly. This fact poses a severe issue to further progress in this exciting research area because ball mill setup and experimental parameters govern how much kinetic energy is transferred to a chemical reaction. In this work, we address the challenge of comparing mechanochemical reaction results by taking the energy dose provided by ball mills as a unified metric into account. In this quest, we applied kinematic modeling to two ball mills functioning under distinct working principles to express the energy dose as a mathematical function of the experimental parameters. By examining the effect of energy dose on the extent of the mechanocatalytic depolymerization (MCD) of lignocellulosic biomass (beechwood), we found linear correlations between yield of water-soluble products (WSP) and energy dose for both ball mills. Interestingly, when a substrate layer is formed on the grinding jar wall and/or grinding medium, a weak non-linear correlation between water-soluble products yield and energy dose is identified. We demonstrate that the chemical reaction’s best utilization of kinetic energy is achieved in the linear regime, which presents improved WSP yields for given energy doses. In the broader context, the current analysis outlines the usefulness of the energy dose as a unified metric in mechanochemistry to further the understanding of reaction results obtained from different ball mills operating under varied experimental conditions.

Mechanochemical synthesis of crystalline U(vi) triperoxide solids

Mechanochemical reaction of UO3 with metal peroxides (M2O2) yields U(vi) triperoxide materials without producing radioactive solvent wastes.

The Effects of the Binder and Buffering Matrix on InSb-Based Anodes for High-Performance Rechargeable Li-Ion Batteries

C-decorated intermetallic InSb (InSb–C) was developed as a novel high-performance anode material for lithium-ion batteries (LIBs). InSb nanoparticles synthesized via a mechanochemical reaction were characterized using X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and energy-dispersive X-ray spectroscopy (EDX). The effects of the binder and buffering matrix on the active InSb were investigated. Poly(acrylic acid) (PAA) was found to significantly improve the cycling stability owing to its strong hydrogen bonding. The addition of amorphous C to InSb further enhanced mechanical stability and electronic conductivity. As a result, InSb–C demonstrated good electrochemical Li-ion storage performance: a high reversible specific capacity (878 mAh·g−1 at 100 mA·g−1 after 140 cycles) and good rate capability (capacity retention of 98% at 10 A·g−1 as compared to 0.1 A·g−1). The effects of PAA and C were comprehensively studied using cyclic voltammetry, differential capacity plots, ex-situ SEM, and electrochemical impedance spectroscopy (EIS). In addition, the electrochemical reaction mechanism of InSb was revealed using ex-situ XRD. InSb–C exhibited a better performance than many recently reported Sb-based electrodes; thus, it can be considered as a potential anode material in LIBs.

Esterification of Cellulose with Long Fatty Acid Chain through Mechanochemical Method

Mechanochemical reaction, a green synthetic esterification route was utilized to prepare long-chain cellulose esters from microcrystalline cellulose. The influence of reaction conditions such as reaction temperature and time were elucidated. Only low dosage of oleic acid, 1-butyl-3-metylimidazolium acetate, and p-toluenesulfonyl chloride were required. The success of modification reaction was confirmed by Fourier transforms infrared spectroscopy as a new absorbance peak at 1731 cm−1 was observed, which indicated the formation of carbonyl group (C=O). Solid-state nuclear magnetic resonance was also performed to determine the structural property and degree of substitution (DS) of the cellulose oleate. Based on the results, increasing reaction temperature and reaction time promoted the esterification reaction and DS. DS values of cellulose oleates slightly decreased after 12 h reaction time. Besides, X-ray diffraction analysis showed the broadening of the diffraction peaks and thermal stability decreased after esterification. Hence, the findings suggested that grafting of oleic acid’s aliphatic chain onto the cellulose backbone lowered the crystallinity and thermal stability.

Mixed valence Sn doped (CH3NH3)3Bi2Br9 produced by mechanochemical synthesis

Bismuth halides with formula A3Bi2X9, where A is an inorganic or organic cation, show desirable properties as solar absorbers and luminescent materials. Control of structural and electronic dimensionality of these compounds is important to yield materials with good light absorption and charge transport. Here we report mechanochemical reaction of (CH3NH3)3Bi2Br9 with SnBr2 at room temperature in air, yielding a material with strong absorption across the visible and near-infrared (NIR) region. We attribute this to mixed valence doping of Sn(II) and Sn(IV) on the Bi site. X-ray diffraction shows no secondary phases, even after heating at 200oC to improve crystallinity. X-ray photoelectron spectroscopy suggests the presence of Sn(II) and Sn(IV) states. A similar approach to dope Sn into the iodide analogue (CH3NH3)3Bi2I9 was unsuccessful.

Mechanically Triggered Carbon Monoxide Release with Turn-On Aggregation-Induced Emission

Polymers that release functional small molecules under mechanical stress potentially serve as next-generation materials for catalysis, sensing, and mechanochemical dynamic therapy. To further expand the function of mechanoresponsive materials, the discovery of chemistries capable of small molecule release are highly desirable. In this report, we detail a non-scissile bifunctional mechanophore (i.e., dual mechano-activated properties) based on a unique mechanochemical reaction involving norborn-2-en-7-one (NEO). One property is the release of carbon monoxide (CO) upon pulsed solution ultrasonication. A release efficiency of 58% is observed at high molecular weights (Mn = 158.8 kDa), equating to ~154 molecules of CO re-leased per chain. The second property is the bright cyan emission from the macromolecular product in its aggregated state, resulting in a turn-on fluorescence readout coincident with CO release. This report not only demonstrates a unique strategy for the release of small molecule in a non-scissile way, but also guides future design of force-responsive aggregation-induced emission (AIE) luminogens.

THERMAL CONTROL OF MECHANOCHEMICAL REACTION

Mechanochemistry studies and explains the processes of chemical and physicochemical transformations that are generated by mechanical action on a substance. When carrying out deep mechanochemical transformations, as a rule, it is necessary to transfer to solid reagents a portion of energy comparable to the energy of interatomic bonds. For this, various machines and apparatus are used, such as extruders, in which mechanical energy is constantly transferred to the crushed material. The article discusses the interaction of two reagents in a simple chemical reaction in the state of a mixture of particles of two types, which occurs during compression of particles having a rough irregular shape, and colliding with each other, forming areas of contact. Significant stress concentrations and heating of the substance with the formation of a new phase arise in these regions. Thermal control of the mechanochemical reaction is to maintain an optimal balance of dissipative heat and heat from the coolant in the worm reactor so that the rate of flow and the final product of the reaction meet the specified specifications. The formulas provided in the article for calculating the coefficient of the rate of mechanochemical reaction, heat transfer between worm reactor and jacket channel, heat exchange between jacket and environment allows to calculate the balance conditions for thermal management. The block diagram of the technological line, which is presented in the article, is more economical in comparison with carrying out the same reaction in a solvent. The economic benefit lies in the elimination of the steps of introducing and removing the solvent from the reaction product. At the end, it is indicated that the mechanochemical reaction of the transformation of a mixture of two dispersed materials consisting of solid particles into a liquid can be realized in continuous conditions in a flow mode in a worm machine. And thermal control of the course of a mechanochemical reaction can be carried out using controlled heat exchange with a coolant in a jacket under conditions of turn-around spatial dispersion.

Study of succinic anhydride amidation by 2-aminothiazol

The reaction between succinic anhydride and 2-aminothiazole was carried out in polar organic solvents (acetone, 1,4-dioxane, isopropanol) and in a mechanochemical reactor. By of X-ray phase analysis, IR, 1H, 13C NMR spectroscopy it was found that in both techniques of carrying out the reaction, the only product was succinamide. It was shown that the process efficiency in the mechanochemical reaction conditions is higher in comparison with the traditional solution’s synthesis. The solid-phase interaction development was proceeded during 45 days after load removed, it was especially intense in the first 10 days.