Heteroatomic Sites on Carbon: Thermal CO Activation and Transformation by Metal-Free Catalysis.

Due to high thermal stability, the selective cleavage of the CO bond in CO, catalyzed by heterogeneous catalysts, is quite challenging, especially in thermal catalytic areas. For the first time, metal-free active sites for thermal CO 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 on the surficial N, B heteroatomic sites of the nanocarbon, providing valuable insights into the reaction mechanism of CO 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 but also provides more opportunities for designing high-efficiency, low-cost, and scalable heterogeneous carbon-based catalysts in thermal CO transformation processes.