Evolution of Zn(II) single atom catalyst sites during the pyrolysis-induced transformation of ZIF-8 to N-doped...

The pyrolysis of zeolitic imidazolate frameworks (ZIFs) is becoming a popular approach for the synthesis of catalysts comprising porphyrin-like metal single atom catalysts (SACs) on N-doped carbons (M-N-C). Understanding the structural evolution of M-N-C as a function of ZIF pyrolysis temperature is important for realizing high performance catalysts. Herein, we report a detailed investigation of the evolution of Zn single atom catalyst sites during the pyrolysis of ZIF-8 at temperatures ranging from 500 to 900 °C. Results from Zn L-edge and Zn K-edge X-ray absorption spectroscopy studies reveal that tetrahedral ZnN₄ centers in ZIF-8 transform to porphyrin-like ZnN₄ centers supported on N-doped carbon at temperatures as low as 600 °C. As the pyrolysis temperature increased in the range 600-900 °C, the Zn atoms moved closer to the N₄ coordination plane. This subtle geometry change in the ZnN₄ sites alters the electron density on the Zn atoms (formally Zn²⁺), strongly impacting the catalytic performance for the peroxidase-like decomposition of H₂O₂. The catalyst obtained at 800 °C (Zn-N-C-800) offered the best performance for H₂O₂ decomposition. This work provides valuable new insights about the evolution of porphyrin-like single metal sites on N-doped carbons from ZIF precursors and the factors influencing SAC activity.