Enhancing catalytic activity and pore structure of metal–organic framework-808 via ligand competition for biodiesel production from microalgal lipids at reduced temperatures

Abstract

Catalysts with hierarchical porous structures and increased active defects play a crucial role in catalyzing the conversion of microalgae lipids. However, the template methods used for pore expansion and the acidification process employed to enhance activity are cumbersome and prone to deactivation. It is necessary to propose a simple and versatile synthetic approach to overcome these challenges. By modulating N,N-dimethylformamide basicity with formic acid, MOF-808 exhibited enhanced coordination of benzene-1,3,5-tricarboxylic acid to Zr-clusters, creating three types of functional defects. These defects increased pore size from 1.63 nm to 5.34 nm and enhanced catalyst acidity by 22.8%, while maintaining high porosity. The active catalytic sites were confirmed to be defect sites (exposed Zr4+) through density functional theory. Compared to regular MOF-808, catalyst MOF-808-3/1 shows enhanced hierarchical porosity and increased acidity, enabling efficient conversions at reduced reaction temperature (100 °C) and pressure (352 kPa) compared to 200 °C and 4036 kPa, respectively.