The accurate identification and manipulation for synergistic atom substitution and vacancy is significant and challenging for the overall water splitting (OWS) and theoretical analysis. Herein, a unique Co(OH)(NO₃) (CoNH) material has been adopted to instantaneously realize oriented atom substitution and vacancies generation through fast impregnation. We found that in alkaline solution, the nitrate groups are prone to dissolve, thus forming nitrate vacancies that are the preferential sites for foreign atoms. Therefore, the controlled atom substitutional doping and vacancies can be simultaneously accomplished. As verification, after dipping in respective solution, S/Se/Mo/P was doped and nitrate deficiencies formed. The atom replacement and vacancy synergistically modulate the electron arrangement, chemical environment, and adsorption capability of host materials, thus boosting electrocatalytic OWS activity. In addition, the precise structure with definite lattice is propitious for the reveal of the structure–property connection. By theory calculation, the optimized electronic structure and adsorption ability of well-defined structures are also uncovered. This present work is expected to shed fresh light on accurate atom incorporation and vacancy engineering, thus achieving a deeper understanding of the structure-composition-property relationship.

协同原子取代和空位的准确识别和操作对于全水分解 (OWS) 和理论分析具有重要意义和挑战性。在此，独特的 Co(OH)(NO ₃）（CoNH）材料已被采用通过快速浸渍瞬间实现定向原子取代和空位产生。我们发现在碱性溶液中，硝酸盐基团容易溶解，从而形成硝酸盐空位，这些空位是外来原子的优先位点。因此，可以同时实现可控的原子置换掺杂和空位。作为验证，在浸入相应溶液后，掺杂了 S/Se/Mo/P 并形成了硝酸盐缺陷。原子置换和空位协同调节主体材料的电子排列、化学环境和吸附能力，从而提高电催化 OWS 活性。此外，具有明确晶格的精确结构有利于揭示结构-性能联系。通过理论计算，还揭示了明确结构的优化电子结构和吸附能力。目前的工作有望为准确的原子结合和空位工程提供新的思路，从而更深入地了解结构-组成-性质关系。