C ₁ -Oxygenates for Carbon Neutrality: A Focused Review on the Production and Application of Methyl Formate and Dimethyl Carbonate with Particular Emphasis on Combustion Kinetics

Oxygenated hydrocarbons show great promise as oxygenated fuel additives and substitutes for conventional petroleum fuels. Among these, the C1-oxygenates methyl formate (MeFo) and dimethyl carbonate (DMC) provide exceptional potential to achieve near-soot-free combustion due to the absence of C–C bonds in their structures, in addition to their ability to significantly reduce net CO2 emissions when applied as e-fuels in a closed carbon cycle. Recent engine experiments with MeFo/DMC blends demonstrated satisfactory performance, further highlighting their practical application potential. Thus, this review comprehensively summarizes recent advances in the production and combustion science of MeFo, DMC, and their mixtures, placing particular emphasis on their reaction kinetics. The review commences with an overview of their physicochemical properties and production pathways, thereby elucidating their potential as renewable alternatives to fossil fuels. Subsequently, a comprehensive evaluation of their fundamental ignition and combustion characteristics is presented. Existing chemical kinetic models for MeFo, DMC, and their blends are examined. Note that DMC is also a crucial electrolyte solvent in lithium-ion batteries. The understanding of its reaction kinetics is therefore important for modeling thermal runaway and enhancing safety as well. Furthermore, this review discusses applications of MeFo and DMC in internal combustion engines and their emission control strategies, highlighting their vital roles in addressing climate change and fostering sustainable transportation solutions. Concluding remarks propose future experimental and numerical research efforts required for improved knowledge about the combustion kinetics of MeFo, DMC, and their blends.