Decoupled Control of CO 2 and Nitrate Reduction Intermediates to Enable Efficient Tandem Urea Electrosynthesis

作者：Jiawei Liu, Ruihuan Duan, Yifan Xu, Chu Zhang, Chade Lv, Erhai Hu, Jiajian Gao, Bo Han, Carmen Lee, Zheng Liu, Li Li, Dongshuang Wu, Man‐Fai Ng, Qingyu Yan · 发表于：ACS Nano · 年份：2025 · DOI：10.1021/acsnano.5c09017 · 被引用次数：22 · 研究领域：Ammonia Synthesis and Nitrogen Reduction、CO2 Reduction Techniques and Catalysts、Covalent Organic Framework Applications

The direct electrochemical coupling of CO 2 and nitrate (NO 3 – ) offers a sustainable alternative to the energy-intensive Bosch–Meiser process for urea synthesis. However, achieving efficient C–N coupling at single active sites remains challenging due to the kinetic mismatch between CO 2 and NO 3 – reduction, as well as the intricate multistep proton-coupled electron transfer process. Here, we present a sacrificial template-based strategy to synthesize a two-dimensional (2D)/zero-dimensional (0D) FeP 0.9 S 2.9– x /Ag 2 S heterostructure catalyst, enabling the tandem coreduction of CO 2 and nitrate for urea electrosynthesis. Electrochemical studies, in situ measurements, and theoretical calculations together demonstrate that the heterostructures with strongly coupled interfaces not only modulate the electronic structure but also enable decoupled control over NO 3 – and CO 2 reduction. FeP 0.9 S 2.9– x offers a moderate conversion rate from NO 3 – to ammonia, generating *NH 2 intermediates while mitigating overhydrogenation to ammonia. Meanwhile, Ag 2 S with optimized loading facilitates efficient conversion of CO 2 to CO, enabling the diffusion and electrophilic attack of CO on *NH 2, thereby forming the critical *CONH 2 intermediate for urea production. As a result, the FeP 0.9 S 2.9– x /Ag 2 S tandem catalyst achieves a high urea yield rate of 1160.9 μg h –1 mg cat –1 with a Faradaic efficiency (FE) of 15.4% at −0.7 vs reversible hydrogen electrode, outperforming the indivi...