Zhao Qinglan, Liu Yushen, Zhang Yuan, Zhu Shangqian, Xu Hongming, Farhadpour Mohammad, Xiao Fei, Xing Minghui, Cao Dapeng, Qin Xueping, Vegge Tejs, Shao Minhua
Department of Chemical and Biological Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, P. R. China.
School of Chemistry and Chemical Engineering, Southeast University, Jiangning District, Nanjing, Jiangsu, 211189, P. R. China.
Adv Sci (Weinh). 2025 Jul;12(27):e2501882. doi: 10.1002/advs.202501882. Epub 2025 May 8.
Electrochemical co-reduction of carbon dioxide and nitrates (CONORR) holds promise for sustainable urea production. However, the sluggish kinetics of the sixteen-electron transfer and unclear mechanistic understanding strongly impede its development. Here, combined experimental and computational approaches are employed to screen a series of metal phthalocyanine as model catalysts (MPcs, M = Zn, Co, Ni, Cu, and Fe) to uncover the activity-selectivity trends in electrochemical CONORR. The theoretical simulations reveal that the thermodynamics of urea synthesis is significantly influenced by key intermediates, where the enhanced adsorption of *HOOCNO, coupled with reduced adsorptions of *N and *COOH, and moderate adsorption of *HO, can significantly promote the urea production. ΔG-ΔG-ΔG+ΔG as a potential descriptor is proposed for predicting the efficiency of CONORR toward urea formation. The findings provide systematic guidance for the future design of high-efficiency catalysts for urea electrosynthesis, addressing a crucial need for sustainable nitrogen fixation.
二氧化碳和硝酸盐的电化学共还原（CONORR）为可持续尿素生产带来了希望。然而，十六电子转移的缓慢动力学以及对反应机理的不明晰理解严重阻碍了其发展。在此，采用实验和计算相结合的方法筛选了一系列金属酞菁作为模型催化剂（MPcs，M = Zn、Co、Ni、Cu和Fe），以揭示电化学CONORR中的活性-选择性趋势。理论模拟表明，尿素合成的热力学受到关键中间体的显著影响，其中HOOCNO的吸附增强，同时N和COOH的吸附减少，以及HO的适度吸附，可显著促进尿素的生成。提出ΔG-ΔG-ΔG+ΔG作为预测CONORR生成尿素效率的潜在描述符。这些发现为未来尿素电合成高效催化剂的设计提供了系统指导，满足了可持续固氮的关键需求。
