Boosting decarboxylation of monomethyl adipate coupling to dimethyl sebacate through Pt electrode at high current density

Abstract

Dimethyl sebacate is an essential organic chemical, yet its conventional high-temperature pyrolytic synthesis process is marked by complexity, energy intensity, environmental pollution, and volatile raw material supplies. Presently, electrochemical synthesis emerges as a promising, environmentally sustainable method for one-step dimethyl sebacate synthesis via anodic decarboxylation coupling with monomethyl adipate. However, the existing process falls short in achieving the desired selectivity and current efficiency, particularly when operating at high current densities, thus impeding its broader industrial adoption. This study, synergizing density functional theory computations with experimental methods, conducts a comprehensive multidimensional analysis of the electrochemical performance at high current densities across four distinct electrode types: Pt plate, RuO2/Ti, PbO2, and graphite electrodes. It underscores the strong electron-orbital hybridization between adsorbed monomethyl adipate and the platinum electrode, resulting in an enhanced propensity for electron transfer at the electrode interface and facilitating the decarboxylation of monomethyl adipate coupling into dimethyl sebacate. Subsequently, through single-factor experiments and response surface methodology, an exhaustive analysis of the various factors influencing the electrolysis process is conducted, including supporting electrolyte, current density, H2O content, neutralization, and monomethyl adipate concentration. The optimal electrolysis operation configuration offers a robust theoretical foundation and technical framework for the large-scale implementation of green, energy-efficient electrochemical synthesis technology for dimethyl sebacate in industrial settings.