Highly efficient metal-free catalyst with unexpected active site for catalytic reactions

Publication in ACS Nano

(c) (2019) American Chemical Society

Researches from the department 'Heterogenous Reactions' have recently reported a highly efficient metal-free catalyst with unexpected active site for catalytic reactions. The work lead by Dr. Yangming Lin and Dr. Linhui Yu from the 'Carbon Synthesis and Applications' group headed by Dr. Saskia Heumann has been published in ACS Nano, an international journal for the communication of comprehensive articles on nanoscience.

The catalytic oxidation is an important reaction in the synthesis of many organic compounds. In the times were sustainable alternatives to simplify synthetic approaches are desired, the finding of new catalytic materials and understanding of the mechanism of this process has been a subject of considerable efforts.

Nitrogen-doped nanocarbon (NDN) as the representative metal-free catalyst has shown promising ability in the catalytic oxidation of alcohols to aldehydes. In contrast to typical catalysts used for this reaction, the reagents do not generate heavy-metal waste. This makes them a promising “green catalyst”, especially in the development of other value-added chemicals from biomass. In example, NDN catalysts might be utilized in the catalytic synthesis of natural products like: intermediates of vitamin E and K3.

Dr. Yangming Lin, the first author of the reported work explains: "In this study, we designed and synthesized NDN material with enriched pyridinic N configuration, within a simple and effective approach. It allowed us to identify the promising capabilities of this catalyst for alcohol and phenol oxidation. We extended the study with in situ measurements, like Nuclear Magnetic Resonance (NMR) and infrared spectroscopy (IR), and supported them with theoretical calculations. Moreover, we used aromatic organic molecules with designated nitrogen species as model catalysts to gain insight into the explicit role of each nitrogen group. Thus, we gained in-depth insights into the active sites and the activation process of those carbon catalysts at a molecular level. It is demonstrated that pyridinic N species play an unexpected role, which differ from the conventional active sites (graphitic nitrogen) only indicated for the aerobic reactions, and thus broaden the concept of active sites in other oxidation reactions."

The researches also appreciate the great collaboration with scientist from Chinese Academy of Sciences, University of Messina (Italy) and Fritz Haber Institute of the Max Planck Society.

Original publication: Lin, Y., Liu, Z., Niu, Y., Zhang, B., Lu, Q., Wu, S., Centi, G., Perathoner, S., Heumann, S., Lu, Y., Su, D.S. (2019). Highly Efficient Metal-Free Nitrogen-Doped Nanocarbons with Unexpected Active Sites for Aerobic Catalytic Reactions ACS Nano https://doi.org/10.1021/acsnano.9b05856