Metal‐Free Boron/Phosphorus Co‐Doped Nanoporous Carbon for Highly Efficient Benzyl Alcohol Oxidation

Abstract An in‐depth understanding of the electronic structures of catalytically active centers and their surrounding vicinity is key to clarifying the structure–activity relationship, and thus enabling the design and development of novel metal‐free carbon‐based materials with desired catalytic performance. In this study, boron atoms are introduced into phosphorus‐doped nanoporous carbon via an efficient strategy, so that the resulting material delivers better catalytic performance. The doped B atoms alter the electronic structures of active sites and cause the adjacent C atoms to act as additional active sites that catalyze the reaction. The B/P co‐doped nanoporous carbon shows remarkable catalytic performance for benzyl alcohol oxidation, achieving high yield (over 91% within 2 h) and selectivity (95%), as well as low activation energy (32.2 kJ mol −1 ). Moreover, both the conversion and selectivity remain above 90% after five reaction cycles. Density functional theory calculations indicate that the introduction of B to P‐doped nanoporous carbon significantly increases the electron density at the Fermi level and that the oxidation of benzyl alcohol occurs via a different reaction pathway with a very low energy barrier. These findings provide important insights into the relationship between catalytic performance and electronic structure for the design of dual‐doped metal‐free carbon catalysts.