Boosting Hydroformylation via Reactant Enrichment in Covalent Triazine Frameworks with Atomically Dispersed Rh

Hydroformylation is one of the most widely applied homogeneous catalytic processes in the chemical industry, constituting the predominant manufacturing platform for aldehyde synthesis at commercial scales. Nevertheless, hydroformylation shares with traditional homogeneous catalysis the inherent limitation of difficult catalyst recovery and recycling. Developing heterogeneous catalysts for such reactions is thus critically needed. Herein, a stable nitrogen-rich covalent triazine framework (CTF) was synthesized via a mild Friedel–Crafts alkylation method and employed as a support for Rh single-atom catalysts (Rh/CTF-TPA). In the hydroformylation of 1-decene, the Rh/CTF-TPA catalyst exhibits an exceptional reaction efficiency (TOF > 1900 h−1), outperforming the homogeneous Rh(CO)2(acac). Experimental and characterization results revealed that the CTF support enhances catalytic performance through two key mechanisms: (1) strong enrichment of reactants within its special structure, and (2) efficient dispersion of Rh single-atom sites stabilized by abundant nitrogen coordination. This work demonstrates a rational design strategy for heterogeneous hydroformylation catalysts by leveraging nitrogen-rich porous frameworks to synergistically optimize metal anchoring and reactant enrichment, offering a promising alternative to conventional homogeneous systems.