Utilization of Keplerate-type polyoxomolybdates {Mo132} supported on hierarchical porous SOM-ZIF-8 as reusable catalyst boosts biodiesel production from acidic soybean oils by simultaneous transesterification-esterifications

Improving the reactant mass transfer on the catalyst surface is a feasible approach to fabricate a robust solid catalyst for efficiently promoting the biomass macromolecules-involving reactions, specifically for biodiesel production by using non-edible acidic oils as feedstocks. In this premise, to reduce the mass transfer resistance, the hierarchical porous SOM-ZIF-8 was firstly synthesized using polystyrene spheres (PS) as templates and then employed as catalyst supports for loading of Keplerate-type polyoxomolybdates {Mo132} to prepare a novel {Mo132}@SOM-ZIF-8 solid acid catalyst. The catalyst characterization results revealed that the active species of {Mo132} clusters were well-dispersed on the SOM-ZIF-8 support and the primary framework of the SOM-ZIF-8 support remained nearly unaltered after the preparation processes. This prepared catalyst featured three-dimensional ordered hierarchical porous structure and dual Bronsted-Lewis acid sites, with a large surface area of 736.26 m2/g and high acidity of 903 μmol/g, presenting high activities for concurrent triglyceride transesterification and free fatty acids (FFAs) esterification. With the acidic soybean oils as feedstocks, 93.9 % of oil conversion and full FFA conversion to biodiesel were achieved over this solid catalyst at 130 °C for 8 h with a catalyst loading of 2 wt%, thus imparting the great potential for a one-pot efficient biodiesel manufacture from the acidic oils to comply with the demand of green and clean production. The synergy between the hierarchical porous structure and the strong acidity emerged, thus boosting the catalytic performance of this solid catalyst for the heterogeneous biodiesel production. The good FFA and moisture-resistance capacity was shown for this catalyst even in the case of moisture content of 3 % and FFA content of 25 %. Further, this catalyst showed excellent reusability without significantly losing its catalytic performance even after five runs, providing a deeper insight into constructing efficient solid catalysts with hierarchical porous structure that are utilized for cost-effective production of biodiesel from the non-edible acidic oils.