Modulation of Self‐Separating Molecular Catalysts for Highly Efficient Biomass Transformations

The energetically viable fabrication of stable and highly efficient solid acid catalysts is one of the key steps in large‐scale transformation processes of biomass resources. Herein, the covalent modification of the classical Dawson polyoxometalate (POMs) with sulfonic acids (‐SO(3)H) is reported by grafting sulfonic acid groups on the POM's surface followed by oxidation of (3‐mercaptopropyl)trimethoxysilane. The acidity of TBA(6)‐P(2)W(17)‐SO(3)H (TBA=tetrabutyl ammonium) has been demonstrated by using (31)P NMR spectroscopy, clearly indicating the presence of strong Brønsted acid sites. The presence of TBA counterions renders the solid acid catalyst as a promising candidate for phase transfer catalytic processes. The TBA(6)‐P(2)W(17)‐SO(3)H shows remarkable activity and selectivity, excellent stability, and great substrate compatibility for the esterification of free fatty acids (FFA) with methanol and conversion into biodiesel at 70 °C with >98 % conversion of oleic acid in 20 min. The excellent catalytic performance can be attributed to the formation of a catalytically active emulsion, which results in a uniform catalytic behavior during the reaction, leading to efficient interaction between the substrate and the active sites of the catalyst. Most importantly, the catalyst can be easily recovered and reused without any loss of its catalytic activity owing to its excellent phase transfer properties. This work offers an efficient and cost‐effective strategy for large‐scale biomass conversion applications.