Heteroatomic Sites on Carbon: Thermal CO₂ Activation and Transformation by Metal‐Free Catalysis

Due to high thermal stability, the selective cleavage of the CO bond in CO 2 , catalyzed by heterogeneous catalysts, is quite challenging, especially in thermal catalytic areas. For the first time, metal‐free active sites for thermal CO 2 activation and transformation are constructed on the nanocarbon surface in this work. The potential H‐assisted cleavage of the activated CO bond to produce CO on the metal‐free catalyst is predicted and further confirmed by its reduction using silane as a hydrogen resource. With in situ infrared spectroscopy and theoretical calculations, the evolution process of CO 2 on the surficial N, B heteroatomic sites of the nanocarbon, providing valuable insights into the reaction mechanism of CO 2 transformation is revealed. This unprecedented finding not only enhances the understanding of the metal‐free catalytic process for the selective cleavage of the CO bond in CO 2 but also provides more opportunities for designing high‐efficiency, low‐cost, and scalable heterogeneous carbon‐based catalysts in thermal CO 2 transformation processes.