Dimethyl Carbonate Research Articles

The influence of P-toluenesulfonyl isocyanate on the solvation structure and solid electrolyte interphase formation on graphite anode under high temperatures

The formation and stability of the solid electrolyte interphase (SEI) play a crucial role in determining the performance and lifespan of lithium-ion batteries (LIBs) at evaluated temperatures. Electrolyte additives have emerged as promising candidates for modulating the formation kinetics and stability of the SEI layer. In this study, molecular dynamics (MD) and ab initio molecular dynamics (AIMD) simulations were employed to investigate the influences of P-toluenesulfonyl isocyanate (PTSI) as an electrolyte additive in the LiPF6/EC/DMC electrolyte on the SEI formation process on the graphite anode under high temperatures. MD simulations revealed that PTSI induces modifications in the solvation structure, resulting in two ethylene carbonate (EC) and two dimethyl carbonate (DMC) molecules in the first solvation shell of Li+. Furthermore, the PTSI additive suppressed the decomposition of solvent molecules and PF6 anions in the LiPF6/EC/DMC/PTSI electrolyte under high temperatures according to the AIMD simulations, contributing to a more stable SEI layer. Moreover, this suppression can be attributed to the reduced reactivity of solvent molecules and salt anions, as evidenced by the enhanced bond strength and decreased bond length. These microscopic insights provide a multi-faceted understanding of the functionality of PTSI additives, facilitating the rational design of novel additives.

Targeted valorization of waste polycarbonate into bisphenol A dimethyl ether

The chemical recycling of waste polycarbonate (PC) plastic to produce high value-added chemicals represents a sustainable and economical approach to its management. Facile methods that utilize the unique structure of the bisphenol A (BPA) unit are expected to be more low-carbon and cost-effective. However, there are few established routes for converting BPA into valuable derivatives while preserving its structure. In this work, we developed a new pathway for the targeted valorization of PC waste into a multifunctional value-added chemical, bisphenol A dimethyl ether (BPAME). Using ionic liquids as catalysts, low-toxicity and environmentally friendly dimethyl carbonate (DMC) as a methyl source, and N-methylpyrrolidone as a co-solvent, we successfully achieved 100 % depolymerization of PC and an impressive 99 % yield of BPAME under mild conditions (150 °C, 6 h). Kinetic studies indicated that the methylation of BPA is the rate-determining step. Moreover, this innovative pathway not only transformed commercial PC waste into BPAME with exceptional selectivity (99 %) and high yield (≥92 %), but also facilitated the efficient methylation of aromatic phenols and amines. This valorization strategy for PC waste disposal offers a promising option for industrial applications.

Visible-Light-Promoted Iron(II)/Lewis Base Catalysis for the Alkylation of Morita-Baylis-Hillman Acetates Using Carboxylic Acids.

A novel photoinduced Fe(OTf)2/2,4,6-collidine-catalyzed alkylation of Morita-Baylis-Hillman (MBH) acetates using carboxylic acids in a regio- and stereoselective manner is reported. This method demonstrates a broad scope, encompassing various carboxylic acids and MBH acetates, including drugs and bioactive molecules, to synthesize densely functionalized cinnamates and acrylates. The reactions are performed in the green solvent dimethyl carbonate under oxidant-free conditions. Based on control experiments, a plausible mechanism involving an Fe(II)-Fe(III)-Fe(II) cycle is proposed.

Advantages of dimethyl carbonate as organic modifier for enantioseparation of novel psychoactive substances in sub/supercritical fluid chromatography

Advantages of dimethyl carbonate as organic modifier for enantioseparation of novel psychoactive substances in sub/supercritical fluid chromatography

Latex-Bridged Inverse Pickering Emulsion for Durable Superhydrophobic Coatings with Dual Antibacterial Activity.

There is agreement that every colloidal structure produces its own set of unique characteristics, properties, and applications. A colloidal phenomenon of latex-bridged water in a dimethyl carbonate (DMC) Pickering emulsion stabilized by R202 hydrophobic silica was investigated for its ability to act as a superhydrophobic coating (SHC) for cellulose substrates. First, various emulsion compositions were screened for their stability and droplet size. The final composition was then cross-examined by cryogenic scanning electron microscopy and optical and fluorescent microscopy to verify the colloidal structure. The drying pattern of the coating was investigated by using labeled samples under a fluorescent microscope and by scanning electron microscopy on a paper substrate. After the final ∼3 μm of dry coating was applied, it exhibited superhydrophobicity (advancing contact angle = 155°) and full functionality after 5 min at room temperature (RT). Coated samples maintained superhydrophobicity after 20 abrasion cycles and mechanical integrity after 50 s of water immersion. The SHC-coated paper demonstrated compatibility with a standard laser printer, and the coated paper demonstrated superhydrophobicity after printing. Finally, a propolis/DMC extract was produced and then analyzed by gas chromatography-mass spectroscopy (GC-MS) and infused into the SHC (PSHC). The newly formed PSHC demonstrated its ability to act effectively against E. coli biofilm and S. aureus planktonic cells and reduce their viability by over 90% and 99.99%, respectively.

Thermophysical study for Binary mixtures of Dimethyl carbonate with Anisole, Butyl vinyl ether, Diisopropyl ether and Dibutyl ether at 303.15, 308.15 and 313.15 K

Ultrasonic velocity, density and viscosity have been determined for the binary compositions of dimethyl carbonate+ butyl vinyl ether, + diisopropyl ether, + anisole and + dibutyl ether at T= 303.15, 308.15 and 313.15 K. The inventive data is applied to assess the excess molar volume VmE, deviation in viscosity Δη and the acoustical parameters namely isentropic compressibility (Ks), free volume (Vf ), free length (Lf ) and internal pressure (πi). The excess or deviation properties are contoured to the Redlich-Kister polynomials and the outcomes are elucidated in terms of molecular interactions present in compositions.

The Role of K2CO3 in the Synthesis of Dimethyl Carbonate from CO2 and Methanol

The synthesis of dimethyl carbonate (DMC) from methanol and CO2 has also received widespread attention, and K2CO3 is usually used as a catalyst in the synthesis of DMC. In this work, the role of K2CO3 in synthesizing dimethyl carbonate (DMC) from methanol and CO2 was revisited. Interestingly, NMR results indicated that K2CO3 can react with methanol to form carbonate CH3OCOO−, an essential intermediate in the synthesis of DMC, which can be transformed into DMC in the presence of CH3I. In other words, K2CO3 can act as not only a catalyst but also a reactant to synthesize DMC from methanol and CO2.

The Origin of Rapid Capacity Loss in 1,1,1‐Trifluoroethyl Methyl Carbonate – Based Lithium‐Ion Battery Electrolytes

Abstract1,1,1‐trifluoroethyl methyl carbonate (FEMC) is a popular non‐flammable solvent for lithium‐ion battery electrolytes, although its high irreversible capacity means it can only be used with film‐forming additives like fluoroethylene carbonate (FEC). This work studies the origin of the high irreversible capacity of FEMC‐containing cells. Scanning electron microscopy and Raman spectroscopy of graphite anodes after charging and discharging in an FEMC electrolyte show evidence of significant physical and chemical graphite degradation, likely caused by solvent co‐intercalation, which is probably responsible for a large portion of the capacity loss. X‐ray photoelectron spectroscopy analysis of the anodes shows very low graphite signals, a sign of graphite degradation, formation of a thick solid electrolyte interphase (SEI), or both. When a small amount of FEC is added to FEMC, co‐intercalation does not occur. FEC reduction occurs at a higher potential versus Li/Li+ than FEMC co‐intercalation. It also forms a significantly different and thinner SEI containing more carbon, less fluorine, and no apparent FEMC decomposition products.

Valorization of Glycerol to Glycerol Carbonate and Glycidol by Different Dialkyl Carbonates Utilizing Tricalcium Aluminate Hexahydrate as Transesterification Catalyst

AbstractIn this study, we report a base‐catalyzed transesterification reaction of glycerol, a waste product of the biodiesel industry, with various dialkyl carbonates, which act both as reactants and solvents, to convert glycerol carbonate into an industrially useful molecular building block. The catalyst, being used for the first time, is also a waste product from industry, present in bauxite residues and in the Portland cement, simply known as tricalcium aluminate. Despite being well‐known and readily available, this solid is only extremely poorly researched catalyst, nevertheless, using dimethyl and diethyl carbonate, glycerol conversion rates >80% and glycerol carbonate yields >60% could be achieved in just 1 h (under air atmosphere and reflux). In a comparison of the performance with other catalysts commonly researched today, as well as with other components of red mud and cements, the results showed that tricalcium aluminate is excellent, cheap, and largely environmentally friendly material for this purpose. Reusability studies of the catalysts have also shown that they provide high conversion and product yields even after repeated use, although different material characterization techniques showed intense glycerol‐catalyst surface interaction and intermediate product formation, the deactivating side effects of which could be avoided by catalyst regeneration steps.

Direct Synthesis of Dimethyl Carbonate from Methanol and CO2 over ZrO2 Catalysts Combined with a Dehydrating Agent and a Cocatalyst

Zirconia nanocrystals as catalysts for the direct synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide have received significant interest recently. In this paper, three zirconia-based catalysts presenting different monoclinic and tetragonal phase contents are prepared and characterized by X-ray diffraction (XRD), N2 adsorption–desorption, transmission electron microscopy (TEM), and temperature-programmed desorption of NH3 and CO2 (NH3-TPD and CO2-TPD). The catalytic performances of these solids are evaluated in terms of DMC production. This production is low when using the bare zirconias, but it is significantly increased in the presence of 1,1,1-trimethoxymethane (TMM) playing the role of a dehydrating agent, which shifts the thermodynamic equilibrium. Moreover, the production of DMC is further improved by adding a second solid catalyst (cocatalyst), the molecular sieve 13X, to accelerate the hydration of TMM. Hence, the molecular sieve 13X plays a dual role by trapping water molecules formed by the reaction of DMC synthesis and providing strong acidic sites catalyzing TMM hydrolysis. To the best of our knowledge, the combination of two solid catalysts in the reaction medium to accelerate the water elimination to obtain higher DMC production from CO2 and methanol has never been reported.

Rapid green analytical methodology for simultaneous monitoring of nitrosamines and semi-volatile organic compounds in water and human urine samples.

Nitrosamines and semi-volatile organic compounds (SVOCs) are carcinogenic contaminants in water and biological matrices. Conventional analytical methods often struggle to detect trace concentrations due to poor extraction efficacies. This study presents a novel, low-cost, in-syringe-assisted fast extraction cum cleanup technique coupled with GC-FID for monitoring four nitrosamines and two SVOCs in drinking water and human urine samples to measure the contamination and exposure levels. This extraction protocol combines a novel green in-syringe liquid-liquid extraction step using dimethyl carbonate as the green extraction solvent, coupled with a semi-automated solid-phase extraction cleanup process. Then, the final extractant is analyzed using gas chromatography-flame ionization detection (GC-FID) for monitoring. The method demonstrated excellent linearity (R2 > 0.998) between 1.5 and 500ngmL⁻1 for all six target compounds. Detection limits ranged from 1.0 to 2.0ngmL⁻1. Extraction recoveries were between 87 and 105% for both urine samples and water samples. Intra-day and inter-day precision were below 9% RSD. The blue applicability grade index evaluation scored 70.0, indicating good practical applicability. The developed analytical protocol offers a sensitive, accurate, low-cost, rapid, and environmentally friendly method for simultaneously quantifying multiple nitrosamines and SVOCs in environmental and human samples. Its performance characteristics and sustainability metrics suggest the potential for broad application in monitoring and exposure studies.

Thermo-kinetic synergy in separating dimethyl carbonate/methanol/water mixtures using ionic liquids-based mixed solvents

The low selectivity of traditional organic solvents and the limited mass transfer efficiency caused by the high viscosity of ionic liquids (ILs) pose challenges in separating of dimethyl carbonate (DMC)/methanol/water mixtures. Therefore, a novel mixed solvent is proposed with a mass ratio of methyl salicylate to 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide of 6:4. The synergistic effects of thermodynamic, kinetic, and economic performance using the mixed solvent are investigated. Comparisons of overall efficiency and total annual cost (TAC) for four process configurations using direct and indirect extractive distillation sequences to produce industrial and battery-grade DMC products are conducted. The results indicate that direct extractive distillation outperforms the indirect sequence, reducing TAC by 6.1–14.3 % for producing industrial-grade DMC and 6.6–15.8 % for battery-grade DMC. Additionally, using mixed solvents in direct extractive distillation is more effective than using pure solvents, enhancing mass transfer coefficients by 2.8–20.9 % for industrial-grade DMC and 1.8–17.8 % for battery-grade DMC. This approach also reduces TAC by 3.2–3.6 % for industrial-grade DMC and 4.7–5.7 % for battery-grade DMC.

Extraction of poly(3-hydroxybutirate) from Priestia megaterium using non-halogenated solvents: A comparative performance analysis

Solvent extraction using chloroform is the most common industrial process for poly(3-hydroxybutyrate) (P(3HB)) recovery from dried biomass, and still a major barrier to expanding the commercial application of this biodegradable biopolymer. Consequently, there is great interest in alternative non-halogenated solvents for this process and some relevant related results are available in the literature for P(3HB) recovery from Gram-negative bacteria. This work evaluated the potential of a set of non-halogenated solvents for the extraction of P(3HB) from Priestia megaterium, a Gram-positive bacterium of great potential for P(3HB) production. Ethyl acetate (EtAc), methyl ethyl ketone (MEK), dimethyl carbonate (DMC), dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (NNDA), 2-heptanone (2-Hp), propylene carbonate (PC), and isoamyl propionate (IAP) were tested. Preliminary solubilization tests using commercial P(3HB) showed that EtAc, MEK, DMC and IAP had lower P(3HB) solubilization capacity (below 0.08 g/L for EtAc, MEK, and DMC; 1.3–2.5 g/L for IAP) than DMSO (65–70 g/L) and PC, 2-Hp and NNDA (>100 g/L). Then, only DMSO, PC, 2-Hp, and NNDA were evaluated in recovery tests with intracellular P(3HB). DMSO was not selective for P(3HB), causing digestion of cell wall components. PC, 2-Hp, and NNDA outperformed chloroform, but NNDA stood out for its remarkably higher recovery (98.5 %, 30 min, 140 ºC).

Enzymatic Methoxycarbonylation of Tyrosol and Hydroxytyrosol.

Tyrosol and hydroxytyrosol are powerful phenolic antioxidants occurring in olive oil and in by-products from olive processing. Due to their high polarity, esterification or other lipophilization is necessary to make them compatible with lipid matrices. Hydroxytyrosol methyl carbonate is a more effective antioxidant than dibutylhydroxytoluene or α-tocopherol and together with tyrosol methyl carbonate exerts interesting pharmacological properties. The purpose of this work was the enzymatic preparation of alkyl carbonates of tyrosol and hydroxytyrosol. A set of 17 hydrolases was tested in the catalysis of tyrosol methoxycarbonylation in neat dimethyl carbonate to find an economically feasible alternative to the recently reported synthesis of methyl carbonates catalyzed by Novozym 435. Novozym 435 was, however, found to be the best performing catalyst, while Novozym 735, pig pancreatic lipase, lipase F-AK and Lipex 100T exhibited limited reactivity. No enzyme accepted 1,2-propylene carbonate as the acylation donor. Under optimized reaction conditions, Novozym 435 was used in the batch preparation of tyrosol methyl carbonate and hydroxytyrosol methyl carbonate in quantitative yields. The enzymatic methoxycarbonylation of tyrosol and hydroxytyrosol can also be used as a method for their selective protection in enzymatic syntheses of phenylethanoid glycosides catalyzed with enzymes comprising high levels of acetyl esterase side activity.

Organic–Inorganic Fertilization Shifts Dissolved Organic Matter Chemodiversity in Runoff From Tropical Cropland: Roles of Soil Nutrient Stoichiometry

ABSTRACTDissolved organic matter (DOM) is a crucial quality indicator for water health. However, it remains unknown how organic–inorganic fertilization differently shifts the DOM chemodiversity in cropland‐impacted runoff, especially the roles of terrestrial nutrient stoichiometry. Here, a field experiment subjected to 7‐year history of four fertilization regimes, that is, unfertilized (CK), chemical fertilization (NPK), straw return (SR), and NPK + SR, was conducted to examine the quantity and chemodiversity of runoff DOM in tropical China. Moreover, the ecological relationships between runoff DOM properties and soil C:N:P stoichiometry were evaluated. Relative to the control treatment, the carbon content (DOC) of runoff DOM increased by 29.20% and 48.82% under SR and NPK + SR treatments, but remained unchanged in NPK treatment. Conversely, the DOM nitrogen content (TDN) only elevated in NPK treatment (262.58%). For DOM chemodiversity, SR treatment was rich in methyl carbon and protein‐like substances, but lacked fulvic‐/humic‐like compounds. NPK treatment increased the hydrophilic compounds like amino acids and polysaccharides, while reducing aromaticity. NPK + SR treatment enhanced DOM's aromaticity, molecular weight and humification due to the enrichment of quinone, ketone and fulvic‐like substances, possibly shaping an oligotrophic aquatic microbial community. Further study revealed that the occurrence of aromatic DOM was positively correlated with soil moisture content, TK (total potassium), total organic carbon and stoichiometric N:P ratio, indicating the contribution of terrestrial straw‐decomposed products. Inversely, the accumulation of hydrophilic substances (e.g., TDN) correlated positively with soil NO3‐N and C:P ratio, indicating the contribution of endogenous DOM.

Few-layered graphene from cathodic exfoliation in binary solvents and application as a protective layer for lithium metal anodes

Electrochemical exfoliation is a top-down method recognized for its environmentally friendly and scalable approach for producing solution-processable graphene. Among its variation, cathodic exfoliation stands out for its potential in generating few-layer graphene with minimal defects. In this study, we developed a cathodic exfoliation method for graphite foil using a binary solvent system to produce graphene with a reduced number of layers. By employing a 0.1 M LiClO4 solution in a dimethyl sulfoxide and dimethyl carbonate solvents mixture at a 1:2 vol ratio, we enhanced the intercalation of solvated lithium ions into graphite, successfully exfoliating graphene with 5–6 layers. The exfoliated graphene exhibited a low defect density (ID/IG ∼0.05) and a C/O ratio of 33.2. Furthermore, when used as a coating on a separator, the exfoliated few-layered graphene (FLG) sheets demonstrated notable performance as a protective layer for Li metal anode in Li metal battery technology.

Synergistic Pd‐Au Catalyst for Selective Electrosynthesis of Dimethyl Carbonate in Conjunction with High‐Rate Redox System

AbstractThis study reports ambient electrosynthesis of dimethyl carbonate with a palladium–gold catalyst. Material screening identifies a region of intermediate‐catalyst binding energy that facilitates interfacial electron and proton transfers for selective carbonylation, achieving a distinct maximum of 92% faradaic efficiency to dimethyl carbonate. Structural and electrochemical analyses suggest that the alloying of palladium and gold effectively modulates the CO* binding energy to the catalytic surface, in accord with subsequent computational studies. With an extended heterogeneous–homogeneous catalytic environment with a halide redox mediator, a remarkable partial current density of 52 mA cm−2 is observed for dimethyl carbonate for 100 h of continuous operation.

Radiocatalytic Synthesis of Acetic Acid from CH4 and CO2.

The C-C coupling of methane (CH4) and carbon dioxide (CO2) to generate acetic acid (CH3COOH) represents a highly atom-efficient chemical conversion, fostering the comprehensive utilization of greenhouse gases. However, the inherent thermodynamic stability and kinetic inertness of CH4 and CO2 present obstacles to achieving efficient and selective conversion at room temperature. Our study reveals that hydroxyl radicals (⋅OH) and hydrated electrons (eaq -) produced by water radiolysis can effectively activate CH4 and CO2, yielding methyl radicals (⋅CH3) and carbon dioxide radical anions(⋅CO2 -) that facilitate the production of CH3COOH at ambient temperature. The introduction of radiation-synthesized CuO-anchored TiO2 bifunctional catalyst could further enhance reaction efficiency and selectivity remarkably by boosting radiation absorption and radical stability, resulting in a concentration of 7.1 mmol ⋅ L-1 of CH3COOH with near-unity selectivity (>95 %). These findings offer valuable insights for catalyst design and implementation in radiation-induced chemical conversion.

Radiocatalytic Synthesis of Acetic Acid from CH4 and CO2

AbstractThe C−C coupling of methane (CH4) and carbon dioxide (CO2) to generate acetic acid (CH3COOH) represents a highly atom‐efficient chemical conversion, fostering the comprehensive utilization of greenhouse gases. However, the inherent thermodynamic stability and kinetic inertness of CH4 and CO2 present obstacles to achieving efficient and selective conversion at room temperature. Our study reveals that hydroxyl radicals (⋅OH) and hydrated electrons (eaq−) produced by water radiolysis can effectively activate CH4 and CO2, yielding methyl radicals (⋅CH3) and carbon dioxide radical anions(⋅CO2−) that facilitate the production of CH3COOH at ambient temperature. The introduction of radiation‐synthesized CuO‐anchored TiO2 bifunctional catalyst could further enhance reaction efficiency and selectivity remarkably by boosting radiation absorption and radical stability, resulting in a concentration of 7.1 mmol ⋅ L−1 of CH3COOH with near‐unity selectivity (>95 %). These findings offer valuable insights for catalyst design and implementation in radiation‐induced chemical conversion.

Keggin structure heteropolyacid-catalyzed phosphinylation of secondary propargyl alcohols with phosphine oxides to γ-ketophosphine oxides.

Phosphotungstic acid with a Keggin structure as an efficient, simple and green catalyst for the phosphinylation of secondary propargyl alcohols with phosphine oxides to afford γ-ketophosphine oxides with up to 88% isolated yield was developed using dimethyl carbonate as a green solvent. Diaryl- or alkylaryl-substituted propargyl alcohols, and diaryl or arylalkylphosphine oxides could tolerate the system, which reduced the catalyst dosage, and avoided the use of multi-components and toxic solvents. More interestingly, phosphotungstic acid exhibited the best activity when 0.58 moles of water were added per mole of HPWA, elevating the yield from 55% to 85%. An 18O labelled product was afforded using trace H218O instead of H2O, indicating the participation of water in the reaction. Besides, our work underscores the importance and effect of a small amount of water, acting to promote the transformation of secondary propargyl alcohols into enones, which should be the real intermediates of the reaction. A mechanism involving a carbocation, Meyer-Schuster rearrangement and Michael addition of enones was proposed.