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However, achieving a balance between structural robustness and dynamic adaptability remains challenging. Herein, we report a new design strategy for self\u2010adaptive electrocatalysts for boosting the electrosynthesis of ammonia by integrating a rigid framework with flexible coordination bonds within a porous coordination polymer (PCP). A rigid\u2010flexible coupling copper pyrazole\u2010based PCP, referred to as Cu\u2010pyNDI, is designed to function as a self\u2010adaptive electrocatalyst that exhibits both structural robustness and dynamic adaptability. Operando x\u2010ray absorption spectroscopy (XAS) reveals that during the reaction, the copper sites in Cu\u2010pyNDI undergo reversible local structural restructuring, resulting in the formation of lower\u2010valence Cu, which serves as potentially active species. Building on the operando XAS findings, we introduced iron doping into Cu\u2010pyNDI to modulate the self\u2010regulating behavior of copper by enhancing the formation of low\u2010valence copper species with lower coordination numbers, which serve as potential active centers, thereby facilitating the generation of the *NO\n                    <jats:sub>2<\/jats:sub>\n                    intermediate. Consequently, Fe\n                    <jats:sub>0.25<\/jats:sub>\n                    Cu\n                    <jats:sub>0.75<\/jats:sub>\n                    \u2010pyNDI demonstrated improved electrocatalytic performance, achieving a Faradaic efficiency of 93% and an ammonia yield of 18847\u00a0\u00b5g h\n                    <jats:sup>\u22121<\/jats:sup>\n                    mg\n                    <jats:sub>cat<\/jats:sub>\n                    <jats:sup>\u22121<\/jats:sup>\n                    in neutral electrolytes, comparable to state\u2010of\u2010the\u2010art electrocatalysts.\n                  <\/jats:p>","DOI":"10.1002\/smll.74909","type":"journal-article","created":{"date-parts":[[2026,8,12]],"date-time":"2026-08-12T06:03:08Z","timestamp":1786514588000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Rigidity\u2010Flexibility Integrated Porous Coordination Polymers via Lattice\u2010Confined Adaptive Evolution for Efficient Neutral Nitrate Reduction to Ammonia"],"prefix":"10.1002","volume":"22","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-3958-044X","authenticated-orcid":false,"given":"Ziqian","family":"Xue","sequence":"first","affiliation":[{"name":"Institute for Integrated Cell\u2010Material Sciences Institute for Advanced Study Kyoto University  Kyoto Japan"},{"name":"School of Advanced Energy Sun Yat\u2010Sen University  Shenzhen China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Maryam","family":"Nurhuda","sequence":"additional","affiliation":[{"name":"Institute for Integrated Cell\u2010Material Sciences Institute for Advanced Study Kyoto University  Kyoto Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Takefumi","family":"Yoshida","sequence":"additional","affiliation":[{"name":"Faculty of Systems Engineering Wakayama University  Wakayama 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