Tailoring Metallic Coordination Centers Enabling Electronic Structure Reconfiguration in Metalloporphyrin‐Based π‐d Conjugated Metal–Organic Framework toward Advanced Potassium‐Ion Batteries

ABSTRACT π‐d conjugated metal–organic frameworks (π‐d c‐MOFs) demonstrate promising potential for application in potassium‐ion batteries (PIBs), whereas developing π‐d c‐MOFs with multiple metallic coordination centers and multipolar redox sites to elucidate the structure–property relationship and improve the performance of PIBs is extremely important and still challenging. Herein, redox‐bipolar metalloporphyrin‐based π‐d c‐MOFs (M 2 [MPP(OH) 8 ], M = Cu or Zn) with dual metallic coordination centers were synthesized and served as cathode materials for PIBs. Different from traditional 2D π‐d c‐MOFs, the special 3D structure endows M 2 [MPP(OH) 8 ] with larger ion storage sites. Moreover, the central porphyrin unit possesses the lone pair electrons and bipolar characteristics, thus generating additional metal coordination sites and enabling simultaneous storage of both anions and cations. As expected, Cu 2 [CuPP(OH) 8 ] cathode shows higher discharge capacity of 225 mAh g −1 at 0.2 A g −1 and longer‐term cycling stability with over 2600 cycles at 5.0 A g −1 , which is superior to Zn 2 [ZnPP(OH) 8 ] counterpart. Most importantly, experimental studies combined with theoretical calculations and in situ characterizations in‐depth elucidate the co‐storage mechanism of both anions and cations. This work presents valuable insights into constructing high‐performance π‐d c‐MOFs cathodes in PIBs through electronic structure reconfiguration strategy.