AgCu bimetallic electrocatalyst for the selective dechlorination of 4-amino-3,5,6-trichloropyridine carboxylic acid

•AgCu bimetallic electrocatalysts were designed for the selective dechlorination of 4-amino-3,5,6-trichloropyridine carboxylic acid.•The optimum Ag16Cu4 exhibits excellent performance with 99.0% selectivity and 98.8% yield of 4-amino-3,6-dichloropyridolinic acid.•The superior performance of Ag16Cu4 stems from the modulated electronic structure by Cu introduction.•This modulation promotes the transfer of charges and reduces the energy barrier of the CH formation. Electrochemical selective dechlorination for the synthesis of high value-added chemical products is an economical and promising technology. Although silver (Ag) electrode is the most representative catalyst in most electrocatalytic dehalogenation reactions, the selectivity for specific reaction needs to be improved. In this framework, AgCu bimetallic electrocatalysts were designed for the selective dechlorination of 4-amino-3,5,6-trichloropyridine carboxylic acid (4-N-3,5,6-TCP) to 4-amino-3,6-dichloropyridolinic acid (4-N-3,6-DCP). The optimum Ag16Cu4 electrode exhibits excellent performance with 99.0% selectivity and 98.8% yield of 4-N-3,6-DCP, surpassing the pure Ag electrode. The combined results of experimental measurements and theoretical calculations indicated that the introduction of Cu modulates the electronic structure of Ag, which not only promoted the transfer of charges, but also reduces the energy barrier of the rate-determining step (the CH formation). In addition, the practicality and scalability of this system was evaluated using a flow-cell reactor. This study demonstrates that AgCu bimetallic catalyst plays a crucial role in determining the selectivity and activity in the electrochemical dechlorination of 4-N-3,5,6-TCP and displays the prospective applications. [Display omitted] The AgCu bimetallic electrode exhibits outstanding selective dechlorination of 4-amino-3,5,6-trichloropyridine carboxylic acid by reduces the energy barrier of the CH formation.