Sequential co-reduction of nitrate and carbon dioxide enables selective urea electrosynthesis

Despite the recent achievements in urea electrosynthesis from co-reduction of nitrogen wastes (such as NO₃^-) and CO₂, the product selectivity remains fairly mediocre due to the competing nature of the two parallel reduction reactions. Here we report a catalyst design that affords high selectivity to urea by sequentially reducing NO₃^- and CO₂ at a dynamic catalytic centre, which not only alleviates the competition issue but also facilitates C-N coupling. We exemplify this strategy on a nitrogen-doped carbon catalyst, where a spontaneous switch between NO₃^- and CO₂ reduction paths is enabled by reversible hydrogenation on the nitrogen functional groups. A high urea yield rate of 596.1 µg mg^-1 h^-1 with a promising Faradaic efficiency of 62% is obtained. These findings, rationalized by in situ spectroscopic techniques and theoretical calculations, are rooted in the proton-involved dynamic catalyst evolution that mitigates overwhelming reduction of reactants and thereby minimizes the formation of side products.