摘要
The electrocatalytic co-reduction of carbon dioxide(CO_(2))and nitrate(NO_(3)^(–))to urea represents a sustainable alternative to energy-intensive industrial synthesis processes.Herein,we report copper-doped cerium oxide nanorods(Cu-CeO_(2))as an efficient catalyst for this reaction,achieving a urea yield of 358.5 mg∙h^(-1)∙g^(-1) at–0.7 V vs.reversible hydrogen electrode with 21.1%Faradaic efficiency.In situ Fourier transform infrared spectroscopy analysis reveals that during electrocatalytic urea synthesis,CO_(2) activation at the catalyst surface generates carbonyl-containing intermediates(^(*)CO),which couple with nitrogenous species(NHx)derived from NO_(3)^(–) reduction.The key coupling reaction intermediate ^(*)NHCO was detected,and the ^(*)NHCO intermediate played a crucial role in promoting C–N bond formation.The stability of this intermediate directly facilitated the successful formation of urea.These findings elucidate the reaction pathway mediated by the Cu-CeO_(2) catalyst,establishing a theoretical foundation for subsequent catalyst design optimization.
基金
supported by the National Natural Science Foundation of China(Grant Nos.22238013 and 22178393)
Hunan Provincial Natural Science Foundation of China(Grant Nos.2023JJ40706 and 2022JJ40354).
