Porous Phosphorus–Nitrogen‐Doped Carbon Material Anchored Rhodium Species for Selective Alkenes Hydroformylation

ABSTRACT The development of high‐performance heterogeneous catalysts for the hydroformylation of olefins to produce aldehydes is significant. The incorporation of heteroatoms into polymeric or carbon nanospheres, aimed at improving catalytic activity and selectivity toward linear aldehydes has motivated extensive research efforts. Herein, we report the design of an N/P co‐doped porous carbon nanomaterial derived from cyclotriphosphazene containing covalent organic framework (COF) for the immobilization of rhodium species. The resulting catalyst exhibited excellent performance in hydroformylation of styrene, achieving 99.9% conversion and 93.1% aldehyde selectivity, with a linear‐to‐branched (l/b) ratio of 1.71. Moreover, it demonstrated remarkable stability over 10 consecutive recycling tests, outperforming most reported Rh‐based catalysts. Mechanistic studies reveal that the introduction of P significantly lowers the energy barrier along the linear aldehyde pathway, with the highest barrier reaching only 0.35 eV. This value was lower than that of branched aldehyde pathway under P‐coordination (0.66 eV), indicating a reversal in regioselectivity favoring linear aldehydes. This work provides a generalizable strategy for the preparation of various metal‐supported carbon‐based catalysts with heteroatoms doping for catalytic applications.