Developing stable electrocatalysts with accessible isolated sites is desirable but highly challenging due to metal agglomeration and low surface stability of host materials. Here we report a general approach for synthesis of single‐site Fe electrocatalysts by integrating a solvated Fe complex in conductive macroporous organic networks through redox‐active coordination linkages. Electrochemical activation of the electrode exposes high‐density coordinately unsaturated Fe sites for efficient adsorption and conversion of reaction substrates such as NO3‐ and H2O. Using the electrode with isolated active Fe sites, electrocatalytic NO3‐ reduction and H2O oxidation can be coupled in a single cell to produce NH3 and O2 at Faradaic efficiencies of 97% and 100%, respectively. The electrode exhibits excellent robustness in electrocatalysis for 200 hours with small decrease in catalytic efficiencies. Both the maximized Fe‐site efficiency and the microscopic localization effect of the conductive organic matrix contribute to the high catalytic performances, which provides new understandings in tuning the efficiencies of metal catalysts for high‐performance electrocatalytic cells.

中文翻译：

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铁配位大孔导电网络电催化硝酸盐还原氨和水氧化的分子布线

开发具有可接近的隔离位点的稳定电催化剂是可取的，但由于金属团聚和基质材料的低表面稳定性而极具挑战性。在这里，我们报告了一种合成单中心铁电催化剂的通用方法，通过氧化还原活性配位键将溶剂化铁配合物整合到导电大孔有机网络中。电极的电化学活化暴露出高密度配位不饱和 Fe 位点，以有效吸附和转化反应底物（例如 NO3-和 H2O）。使用具有隔离活性 Fe 位点的电极，电催化 NO3 还原和 H2O 氧化可以在单个电池中耦合，以分别达到 97% 和 100% 的法拉第效率产生 NH3 和 O2。该电极在200小时的电催化中表现出优异的鲁棒性，催化效率下降很小。最大化的铁位效率和导电有机基质的微观局域化效应都有助于提高催化性能，这为调节高性能电催化电池金属催化剂的效率提供了新的理解。