Dimethyl Carbonate Research Articles

Abstract A per‐ and polyfluoroalkyl substances (PFAS) free electrolyte formulation for the high voltage lithium nickel manganese oxide (LNMO)||silicon‐graphite (SiGr) per‐ and polyfluoroalkyl substances (20 wt.% silicon) cell chemistry is developed. The high upper cut‐off voltage of 4.9 V, together with the substantial volume expansion of the silicon‐graphite negative electrode, imposes stringent demands on the electrochemical stability of the electrolyte. A newly developed PFAS free electrolyte formulation incorporating lithium difluoro(oxalato)borate (LiDFOB) alongside cost‐effective organic carbonate solvents ethylene carbonate (EC) and ethyl methyl carbonate (EMC) enables stable operation of LNMO‖SiGr cell chemistry. Improved galvanostatic cycle life from 145 cycles to 245 cycles (69 %) can be achieved in the presence of 4 wt.% LiDFOB. LiDFOB effectively suppresses the transesterification often observed in organic carbonate‐based electrolytes by scavenging lithium alkoxides and leads to a reduction of transition metal (TM) dissolution. These properties contribute to the formation of an effective solid electrolyte interphase (SEI) and cathode electrolyte interphase (CEI), resulting in improved galvanostatic cycling stability and overall electrochemical performance. The developed PFAS free electrolyte formulation constitutes a promising pathway for high‐voltage lithium ion cells, combining environmental safety with high electrochemical performance.

Abstract For the first time, the immobilization of Lewis base molecular catalysts is demonstrated on lignocellulosic bamboo shavings for synthetic applications, focusing on the valorization of CO 2 and its derivatives. Two types of catalysts are immobilized on bamboo shavings: covalent functionalization using isocyanate chemistry is employed to prepare Bamboo supported Hexaethylenedicarbamate ethyl methyl imidazolium iodide [Bamboo@HMEMIM][I] , while a silane‐based approach is applied to obtain Bamboo supported 1,5,7‐Triazabicyclo[4.4.0]dec‐5‐ene [Bamboo@TBD] . Both materials are fully characterized through elemental analysis, FT‐IR, TGA, and Scanning Electron Microscopy (SEM). The first catalyst, [Bamboo@HMEMIM][I] , promoted the cycloaddition of CO 2 with epoxide, achieving 100% conversion and complete selectivity toward cyclic carbonates under optimized conditions (2.8 mol% catalyst, 10 bar CO 2 , at 70 °C for 16 h). This catalyst also demonstrates good recyclability, showing a decrease in activity only after four consecutive cycles (74% yield in the fourth cycle, 61% in the fifth). The reaction scope demonstrates its broad applicability for other epoxides (Y = 86−100%). The second catalyst is applied to the synthesis of glycerol carbonate through cycloaddition between dimethyl carbonate (DMC) and glycerol. Optimized conditions (5 mol% catalyst, 10:1 DMC:glycerol ratio, at 100 °C for 16 h) achieves 100% conversion and 69% selectivity for glycerol carbonate. In this case the degradation of catalysts by Phanerochaete chrysosporium is investigated.

Abstract Vinylene carbonates (also referred as endo‐vinylene carbonates) were prepared from α‐hydroxyketones and dimethylcarbonate as a cheap and safe carbonyl source. The reaction is performed neat at 90 °C and is catalyzed by an imidazolium salt bearing a hydrogenocarbonate counter‐ion, thus avoiding the need of an external base. The equilibrium was shifted toward the formation of the desired products by removal of methanol using 4 Å molecular sieves, placed outside the reaction vessel. Under these conditions, a range of symmetrical and unsymmetrical, aryl and alkyl vinylene carbonates was prepared with 10%–93% isolated yield (22 examples). A ten‐fold scale‐up experiment was also performed in a Soxhlet apparatus using benzoin as a starting material and the desired vinylene carbonate was obtained with 92% yield. This protocol provides a convenient access to vinylene carbonates on a multi‐gram scale.

1-Butyl-1-methylpyrrolidinium-based ionic liquids for integrated CO2 absorption and transformation into dimethyl carbonate

Ultra-low concentration and flame-retardant electrolyte for next-generation lithium metal batteries.

Carbonate esters as green alternatives in chromatographic separations.

Effect of lattice distortion of CeO2 on direct synthesis of dimethyl carbonate from CO2 and methanol

Green dimethyl carbonate production feasibility based on technical and environmental considerations

Energy-Saving Design for Dimethyl Carbonate Production by Combining with Various Special Distillation Routes of Reactive Distillation

Designing zwitterionic-polysaccharide network hydrogels by covalent and non-covalent functionalization for drug delivery applications.

Chemical and biological recycling of spent polyesters is of great significance for solving problems caused by their accumulation, but generally suffering from requirements for high temperature, specific catalysts or enzymes, and incomplete depolymerization in most cases. Here, we report a novel strategy for complete depolymerization of polyesters (e.g., poly(ethylene terephthalate), PET) with dialkyl carbonates (e.g., dimethyl carbonate, DMC) into monomers over halide salts (e.g., tetrabutylammonium chloride, [N4444]Cl) under mild conditions. We demonstrate that PET can be completely degraded into dimethyl terephthalate (DMT) using DMC over [N4444]Cl at temperatures of 80∼120 °C. Based on this reaction, we have achieved highly efficient and complete depolymerization of PET in various PET blend textiles into DMT while preserving the structural integrity of other components including natural and synthetic components. Mechanistic studies reveal the key role of methoxy anion derived from DMC in cleaving the acyl C─O bond of polyesters. Techno-economic assessment for recycling of spent PET wastes demonstrates excellent economic profit.

Understanding Surface Properties in CeO ₂ Catalysts for the Synthesis of Dimethyl Carbonate: A Combined In Situ IR and NEXAFS Study

During thermal runaway in lithium-ion batteries (LIBs), vaporised electrolytes and their additives are vented into the environment along with battery vent gases (BVG). However, most existing studies analyse the combustion of BVG without considering the role of electrolytes, which may lead to research conditions that fail to accurately reflect real-world scenarios. This study addresses this gap by investigating the effects of dimethyl carbonate (DMC), a common LIB electrolyte, and a novel flame retardant additive, di (2, 2, 2-trifluoroethyl) carbonate (DtFEC), on the explosion limit characteristics of BVG at typical formulations reported in the literature. An innovative chemical effects quantification methodology and kinetic analysis were employed to uncover the underlying mechanisms influencing these phenomena. The results indicate that the addition of DMC and DtFEC transforms the explosion limit curve from a Z-shaped pattern to a monotonic one. Specifically, DMC inhibits reactions at the first and second explosion limits by competing with H radicals, while it enhances reaction activity at the third explosion limit due to the production of reactive species. The introduction of DtFEC results in two novel phenomena, a bulge phenomenon in the explosion limit curve and a leftward shift of the negative temperature coefficient (NTC), which are driven by the interaction between the reaction-thermal effect (RTE) and reaction-radical effect (RRE). As the strong inhibitory region expands, the NTC continues to shift leftward, eventually eliminating the bulge phenomenon. These findings provide new insights into the autoignition and suppression mechanisms of LIB vent gases.

ABSTRACTThis study reports the development of a novel amino‐functionalized ionic liquid catalyst, namely 1‐butyl‐3‐methylimidazolium amino triazole ([EMIM]ATZ), for the efficient and sustainable synthesis of ethyl methyl carbonate (EMC) via transesterification of dimethyl carbonate (DMC) and ethanol (C2H5OH) at room temperature. Addressing the limitations of conventional catalytic systems that require elevated temperatures (> 75°C), [EMIM]ATZ achieves 62% DMC conversion and 56% EMC yield within 8 h under room temperature (25°C), while conventional ionic liquids ([EMIM]Cl, [EMIM]BF4, [EMIM]PF6 etc.) showed almost no activity at room temperature. The catalyst's superior activity stems from its strong basicity (pH ≈ 9.2) and enhanced CO2 absorption capacity (200 mg·g−1), which synergistically activate C2H5OH and stabilize reaction intermediates. Structural characterization via FTIR and thermogravimetric analysis (TGA) confirmed the catalyst's thermal stability and recyclability, with no significant degradation observed over five reuse cycles (89% activity retention). In addition, the ionic liquid was also able to catalyze the synthesis of methyl propyl carbonate (PMC) and methyl butyl carbonate (BMC) at room temperature.

Expanding the use of green solvents for the isolation of melittin from honeybee venom.

Abstract The applicability of sodium containg titanate nanotubes as catalyst powder for the glycerol carbonate (GLC) formation using glycerol (GL) as a main reactant and as a solvent dimethyl carbonate (DMC) was examined. The sodium titania nanotubes were prepared using hydrothermal method, followed by low temperature calcination. The performance of catalyst depended on the basicity of the material, to find out this CO2-TPD (temperature-programmed desorption) carried out. Sodium titanate nanotubes (NaTNT) showed good activity with 92.6% conversion and also very good selectivity (100%) for GLC compared to the pure TiO2. Further more studie on reaction parameters carried out for optimization (reaction temperature (T), time (t), DMC/GL molar ratio, and catalyst amount). The present catalyst showed good recyclability until 5 cycles, with a small amount of GL conversion decreased. Graphical Abstract

Abstract This study presents a sustainable and efficient visible‐light‐driven organophotocatalytic strategy for transforming the methylene carbon of barbituric acids into valuable hydrazones and spirocyclic products. The reaction proceeds smoothly under mild conditions by utilizing eosin Y as a green photocatalyst and atmospheric oxygen as the sole oxidant. This method provides an environmentally friendly alternative to traditional approaches and offers intriguing mechanistic insights into umpolung C(sp3)‐H functionalization, thereby paving the way for novel reactivity in barbiturate chemistry.

In this work, ternary liquid-liquid equilibrium (LLE) was measured for water (H2O) + dimethyl carbonate (DMC) + 1-ethyl-3-methylimidazolium ([Emim][MeSO3]) and methanol (MeOH) + DMC + [Emim][MeSO3] mixtures at 293.15 K at atmospheric pressure. LLEs were modelled utilizing COnductor-like Screening MOdel for Real Solvents (COSMO-RS) and non-random two-liquid (NRTL) models. COSMO-RS was utilized to provide insight into interactions at molecular level through chemical potentials corresponding to the sigma profile and predicted excess enthalpies. The nature of COSMO-RS accuracy was qualitative, while NRTL had an accuracy of 0.013 and 0.030 root mean square deviation for LLE of H2O + DMC + [Emim][MeSO3] and MeOH + DMC + [Emim][MeSO3] mixtures, respectively. Hydrogen bonding behavior explained favorable [Emim][MeSO3]-H2O and -MeOH interactions. These interactions might be mainly due to strong hydrogen bond donor interaction between [MeSO3] anion-H2O and -MeOH. The unfavorable [Emim][MeSO3]-DMC interaction was explained by electrostatic repulsion, possibly arising from repulsion between [MeSO3] anion and DMC oxygens.

Forced ignition of lithium-ion batteries vent gases containing dimethyl carbonate and di (2, 2, 2trifluoroethyl) carbonate

On the use of ethylene carbonate as a green solvent in mobile phases.