Transforming CO Poisoning into a Critical Step for Electrocatalytic C─N Coupling to Urea in a Carbon‐Dot‐Dominated Nanoreactor
Dongxu Zhang, Deli Jiang, Baodong Mao, Yanhong Liu, Qitao Chen, Haitao Li, Lei Xing, Hui Huang, Wei Zhang, Weidong Shi, Zhenhui Kang
Abstract
Abstract Modern catalysis science has traditionally viewed carbon monoxide (CO) poisoning negatively due to its detrimental effects, such as the deactivation of metal sites. Here, we demonstrate a transformative approach by converting CO poisoning into a beneficial strategy to achieve high activity and selectivity in urea electrosynthesis. We designed a multiscale and multisite nanoreactor composed of copper–carbon dots (Cu‐CDs) and bornite (Cu 5 FeS 4 ), which exploits CO‐poisoned iron sites as anchors to facilitate efficient multi‐species integration. This nanoreactor configuration delivers an unprecedented C urea ‐ selectivity of 100%, a high urea yield rate of 1131.84 µg h −1 mg cat −1 and a Faradaic efficiency of 42.35% at an ultra‐low potential. Consequently, the catalyst achieves exceptional dual benefits of a high yield rate and low energy consumption of 31.18 kWh kg urea −1 , outperforming all previously reported earth‐abundant electrocatalysts. Mechanistic studies and theoretical calculations reveal that the strong interaction between Fe and *CO, coupled with spatially separated yet adjacent Fe, Cu 1 , and Cu 2 sites, enables stepwise conversion from *CO to *CONH 2 and subsequently to *CO(NH 2 ) 2 within the nano‐confined space dominated by Cu‐CDs. This work provides a groundbreaking catalyst design strategy by effectively harnessing CO poisoning for enhanced electrocatalytic performance.