Fine-tuning N-doped species of C catalysts for 98% current efficiency of electrocatalytic decarboxylation into hindered ether

Regulating the interaction between the substrate and electrode is crucial for maximizing catalytic performance. In this study, we developed a method for controlling the sintering temperature and introducing H₂O₂ post-treatment to modulate the N-doping of C catalysts, enhancing the interaction between the substrate and electrode to cause a radical reaction, thereby promoting electrocatalytic decarboxylation. When 10 g of feedstock was used, the electrocatalytic system exhibited 9.4- and 4.2-fold increases in productivity and current efficiency, respectively, compared with the conventional method. A systematic investigation combining experiments and theoretical calculations revealed that pyridine N-oxide units not only promote bridging adsorption of the substrate and the formation of a substrate-enriched electric layer but also the transfer of mass and electrons, generating more reactive carboxyl radicals. The electrocatalytic system delivers a current efficiency of 98%, which is exceptional compared to previously reported electrocatalysts. The system is in line with the development trend of the green chemical industry, combining flow reactors and photovoltaic technology. This study offers valuable insights and guidance for advancing electrocatalytic organic synthesis for future industrial applications.