近日，中国科学院过程工程研究所王丹团队报道了中空多壳结构中捕获诱导富集用于高效氨电合成。2026年3月24日出版的《美国化学会志》发表了这项成果。

电化学硝酸盐还原是合成氨的可持续途径，但其发展受限于两大瓶颈：转化效率受制于原位硝酸盐富集不足这一根本限制，以及工况条件下催化机理的动态演变难以捉摸。

研究组报道了一种CuO空心多壳层结构（CuO-HoMS），该结构可作为自发预富集的微纳米反应器，能够以卓越的效率富集、限域并转化硝酸盐。其中，三层壳的CuO-HoMS（3s-CuO-HoMS）在多种催化剂中实现了最优性能：在相对于可逆氢电极-0.4 V的电位下，法拉第效率达96.4 ± 0.9%，氨产率为6316.3 ± 96.1 mmol·g_cat^-1·h^-1。原位共聚焦激光扫描显微镜直接可视化了NO₃^-在分层三腔反应器内的快速持续富集过程，这种增强的阴离子可及性显著降低了过电位，并促进了高效产氨。

原位XAS、拉曼、FTIR及DEMS等表征技术共同揭示了3s-CuO-HoMS的动态演变过程，捕获了含氮中间体，并结合氮源的¹⁵N同位素示踪，推导出令人信服的反应路径。该工作为在特定条件下设计阴离子富集的微纳米反应器，以及阐明工况条件下硝酸盐还原的动态演变机制提供了指导。

附：英文原文

Title: Confinement-Induced Enrichment in Hollow Multishelled Structure for High-Efficiency Ammonia Electrosynthesis

Author: Di Li, Yani Chai, Qian Xiao, Jiayu Zhao, Chang Chen, Jiawei Wan, Ranbo Yu, Dan Wang

Issue&Volume: March 24, 2026

Abstract: Electrochemical nitrate reduction represents a sustainable route for ammonia synthesis, yet its advancement is hampered by two bottlenecks: the fundamental limitation on conversion efficiency stems from inadequate in situ nitrate enrichment and the elusive dynamic evolution of catalytic mechanisms under operational conditions. Here, we report a CuO hollow multishelled structure (CuO-HoMS) that functions as a spontaneous pre-enrichment micronanoreactor capable of enriching, confining, and converting nitrate with exceptional efficiency. The CuO-HoMS with triple shells (3s-CuO-HoMS) achieves a champion Faradaic efficiency of 96.4 ± 0.9%, and an ammonia yield of 6316.3 ± 96.1 mmol·gcat–1·h–1 at 0.4 V versus RHE among various catalysts. In situ confocal laser scanning microscopy directly visualized the rapid and sustained enrichment of NO3– within the stratified three-cavity reactor, with this enhanced anionic accessibility significantly reducing the overpotential and boosting efficient ammonia production. In situ XAS, Raman, FTIR, and DEMS collectively uncovered the dynamic evolution of 3s-CuO-HoMS, captured N-containing intermediates, and deduced a convincing reaction pathway validated by 15N isotopic tracing of the nitrogen source. This work offers guidance for designing anion-rich micronanoreactors under specific conditions and for elucidating the dynamic evolution mechanisms of nitrate reduction under operational conditions.

DOI: 10.1021/jacs.6c01046

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.6c01046