近日，中国科学院深圳先进院杨新春团队报道了离子有机笼促进电催化硝酸还原为氨的界面电荷调节微环境。相关论文发表在2026年4月21日出版的《德国应用化学》杂志上。

氨对于农业和工业至关重要，然而哈伯-博世法能耗高且碳排放量大。电化学硝酸盐还原反应通过将氨合成与水修复相结合，提供了一种可持续的替代方案。然而，硝酸根吸附弱、析氢竞争反应以及催化剂微环境不理想等挑战阻碍了其性能。

研究组报道了一系列电催化剂：Pd⊂QA-Cage^x+（x = 24、12、6），通过将钯簇封装在季铵化有机笼内构建而成。这些离散的宿主结构能够实现均匀的金属簇限域，并精确控制界面微环境。增加笼的电荷密度可富集界面硝酸根浓度，使钯的d带中心上移，并增强*NO₃的活化。同时，电势驱动的电子从抗衡离子（Cl^-）转移到–NH₂⁺–，在笼骨架中产生稳定自由基，这些自由基介导水的活化形成氢自由基（H•），随后溢流到钯位点，加速中间体的氢化。

优化后的Pd⊂QA-Cage²⁴⁺在中性电解质中实现了95.44%的法拉第效率和25.70 mg h^-1 mg_cat^-1的氨产率，性能优于低电荷类似物。此外，该催化剂能够去除富营养化海水中超过99.4%的硝酸盐，使硝酸根浓度降至低于饮用水标准。这项工作引入了离子笼作为可编程的界面修饰剂，提供了一种调控电化学微环境、提升电催化硝酸盐还原性能的超分子策略。

附：英文原文

Title: Interfacial Charge-Regulated Microenvironments Enabled by Ionic Organic Cages for Boosting Electrocatalytic Nitrate Reduction to Ammonia

Author: Shuyuan Li, Jun-Hao Zhou, Shi-Long Han, Doufeng Wang, Ying-Ying Yu, Jun-Yu Li, Si-Hua Liu, Xiaojie Chen, Xinchun Yang, Jian-Ke Sun

Issue&Volume: 2026-04-21

Abstract: Ammonia (NH3) is essential for agriculture and industry, yet the Haber–Bosch process is energy-intensive and carbon-emissive. Electrochemical nitrate reduction reaction (NO3RR) offers a sustainable alternative by coupling NH3 synthesis with water remediation. However, challenges such as weak NO3 adsorption, competing hydrogen evolution, and suboptimal catalyst microenvironments hinder performance. Here, we report a family of electrocatalysts, PdQA-Cagex+ (x = 24, 12, 6), constructed by encapsulating Pd clusters within quaternized organic cages. These discrete hosts enable uniform metal cluster confinement and precise control over the interfacial microenvironment. Increasing cage charge density enriches interfacial NO3 concentration, upshifts Pd d-band center, and enhances *NO3 activation. Simultaneously, potential-driven electron transfer from the counterion (Cl) to –NH2+– generates stable radicals in the cage skeleton, which mediate water activation to form hydrogen radicals (H) that spill over to Pd sites, accelerating intermediate hydrogenation. The optimized PdQA-Cage24+ delivers a Faradaic efficiency of 95.44% and an NH3 yield of 25.70 mg h1 mgcat1 in neutral electrolytes, outperforming its lower-charge analogs. Moreover, it enables > 99.4% nitrate removal from eutrophic seawater, reducing NO3 concentrations below potable water standards. This work introduces ionic cages as programmable interfacial modifiers, offering a supramolecular strategy to regulate electrochemical microenvironments and boost electrocatalytic NO3RR performance.

DOI: 10.1002/anie.4155022

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.4155022