A Click Chemistry Strategy Toward Spin‐Polarized Transition‐Metal Single Site Catalysts for Dynamic Probing of Sulfur Redox Electrocatalysis

Abstract Catalytic conversion of lithium polysulfides (LiPSs) is a crucial approach to enhance the redox kinetics and suppress the shuttle effect in lithium–sulfur (Li–S) batteries. However, the roles of a typical heterogenous catalyst cannot be easily identified due to its structural complexity. Compared with the distinct sites of single atom catalysts (SACs), each active site of single site catalysts (SSCs) is identical and uniform in their spatial energy, binding mode, and coordination sphere, etc. Benefiting from the well‐defined structure, iron phthalocyanine (FePc) is covalently clicked onto CuO nanosheet to prepare low spin‐state Fe SSCs as the model catalyst for Li–S electrochemistry. The periodic polarizability evolution of Fe‐N bonding is probed during sulfur redox reaction by in situ Raman spectra. Theoretical analysis shows the decreased d‐band center gap of Fe (Δd) and delocalization of d _xz /d _yz after the axial click confinement. Consequently, Li–S batteries with Fe SSCs exhibit a capacity decay rate of 0.029% per cycle at 2 C. The universality of this methodological approach is demonstrated by a series of M SSCs (M = Mn, Co, and Ni) with similar variation of electronic configuration. This work provides guidance for the design of efficient electrocatalysis in Li–S batteries.