Hydroformylation of 1‐butene to N‐pentanal on Co‐based Materials Derived from ZIF‐67: Optimization of Pyrolysis Conditions and DFT Study

Abstract We prepared the Co‐based materials via the pyrolysis of ZIF‐67 at low temperature (250 °C~350 °C), and obtained the optimum catalyst ZIF‐67‐Sg‐350‐10 with the conversion of 1‐butene, aldehyde selectivity and n/i ratio of 94.9 %, 77.1 % and 2.2, respectively. The conversion of 1‐butene and aldehyde selectivity obviously increased with the increasing pyrolysis temperature and pyrolysis time. It was found that the interaction between the Co cluster and N‐doped carbon composites could improve the hydroformylation activity. Different catalyst models were built to investigate the active centers (Co) in the derived materials. The Co‐N4 surface was the best catalyst model with the lowest hydrogen insertion reaction energy barrier (0.37 eV).