Reductive Formylation of Nitroarenes using HCOOH over Bimetallic C−N Framework Derived from the Integration of MOF and COF

Abstract CoZn embedded C−N framework is prepared by the carbonization of CoZn containing MOF integrated with COF porous architecture in Ar atmosphere. The graphitic nature of porous carbon is confirmed from Raman analysis. The porosity and nanostructure information are retrieved from N 2 ‐sorption and transmission electron microscopic analysis, respectively. The incorporation of different metals and their oxidation states and types of nitrogen present in the C−N framework are confirmed from X‐ray photoelectron spectroscopy. The basicity of the materials is determined from a CO 2 ‐temperature programmed desorption. ZnCo embedded C−N framework exhibits excellent activity in the selective reductive formylation using HCOOH. For comparison, more than 15 materials are prepared, and their activities are compared. Several control experiments are performed to establish a structure‐activity relation. The recycling experiment, hot‐filtration test, and poisoning experiment demonstrate the metal embedded porous C−N framework‘s recyclability and stability. A reaction mechanism for the reductive N‐formylation of nitroaromatics is presented based on structure‐activity relationship, control reactions, and physicochemical characterizations. The development of interesting MOF‐COF‐derived metal nanoclusters embedded C−N framework for selective reductive formylation of nitroaromatics using formic acid will be highly attractive to catalysis researchers and industrialists.