Dynamically Unveiling Metal–Nitrogen Coordination during Thermal Activation to Design High‐Efficient Atomically Dispersed CoN4 Active Sites

We elucidate the structural evolution of CoN₄ sites during thermal activation by developing a zeolitic imidazolate framework (ZIF)-8-derived carbon host as an ideal model for Co²⁺ ion adsorption. Subsequent in situ X-ray absorption spectroscopy analysis can dynamically track the conversion from inactive Co-OH and Co-O species into active CoN₄ sites. The critical transition occurs at 700 °C and becomes optimal at 900 °C, generating the highest intrinsic activity and four-electron selectivity for the oxygen reduction reaction (ORR). DFT calculations elucidate that the ORR is kinetically favored by the thermal-induced compressive strain of Co-N bonds in CoN₄ active sites formed at 900 °C. Further, we developed a two-step (i.e., Co ion doping and adsorption) Co-N-C catalyst with increased CoN₄ site density and optimized porosity for mass transport, and demonstrated its outstanding fuel cell performance and durability.