Accelerating industrial-level CO electroreduction kinetics on isolated zinc centers sulfur-boosted bicarbonate dissociation

Improving the proton transfer rate in the proton-coupled electron transfer process is the key to accelerating the reaction kinetics of CO 2 electroreduction (CO 2 ER). However, the synchronous enhancement of proton feeding and CO 2 activation are hardly achieved over the single active site, making rapid conversion with high product selectivity a considerable challenge. Herein, we develop an isolated zinc site embedded in nitrogen, sulfur co-doped hierarchically porous carbon (denoted as Zn-NS-C) electrocatalyst toward CO 2 ER, in which central Zn-N 4 active sites are associated with adjacent S dopants in Zn-NS-C. Kinetic experiments combined with in situ spectroscopy unveil that the auxiliary S sites promote bicarbonate dissociation kinetics for proton feeding and atomically dispersed Zn-N 4 sites are likely active centers for the CO 2 ER. Theoretical calculations reveal the synergistic effects of S and Zn-N 4 sites that improve the proton transfer rate and boost the reaction kinetics of *CO 2 protonation to form *COOH. As a result, this catalyst delivers an excellent CO 2 ER performance with near-unity CO selectivity at an industrial-level current density of 200 mA cm −2 and a high turnover frequency of 11 419 h −1 . Furthermore, the high CO productivity on the Zn-NS-C was confirmed by the highly increased partial C 2 H 4 current density in the Zn-NS-C/Cu tandem catalyst. A hierarchically porous carbon electrocatalyst containing isolated Zn sites and N/S dopants was developed for simultaneously facilitating bicarbonate dissociation and CO 2 protonation, achieving high CO 2 ER kinetics at industrial current density.