Rationally developing millimetric metal catalysts with tailored electron function is crucial for water decontamination, but challenges remain due to insufficient understanding on their electronic structure engineering and the underlying mechanism. Here, through constructing bonded Co-O-Al unit sites on the millimetric γ-AlO spheres, we report a feasible and scalable strategy of modulating the 3 electron configurations and spin states of supported tetrahedral and octahedral cobalt cations just by adjusting the radius of support curvature. The tetrahedral and octahedral cobalt centers with tailored electron spin states showed a synergism in peroxymonosulfate activation to generate SO and reactive oxygen (O*), in which the latter was converted into O and O. The electronic structure-oriented spin catalysis affected the formation of reactive species and the pathway of pollutant degradation. This work will stimulate the design and mass production of macroscopic spin catalysts with superior activity, reusability and stability for catalytic water purification.

中文翻译：

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自旋态定制的四面体和八面体钴中心位于毫米钴铝氧化物催化剂上，作为协同过一硫酸盐活化的双位点

合理开发具有定制电子功能的毫米金属催化剂对于水净化至关重要，但由于对其电子结构工程和潜在机制的了解不足，挑战仍然存在。在这里，通过在毫米级γ-Al2O球上构建键合的Co-O-Al单元位点，我们报告了一种可行且可扩展的策略，仅通过调整支撑半径即可调节支撑四面体和八面体钴阳离子的3个电子构型和自旋态曲率。具有定制电子自旋态的四面体和八面体钴中心在过一硫酸盐活化中表现出协同作用，生成SO和活性氧（O*），其中后者转化为O和O。电子结构导向的自旋催化影响了活性物种和污染物降解途径。这项工作将促进具有优异活性、可重复使用性和稳定性的宏观自旋催化剂的设计和大规模生产，用于催化水净化。