In the present study, a facile solvothermal method was used for the synthesis of silicotungstic acid (HSiW) immobilized on Ce-based metal organic framework (Ce-BDC) and embedded in Zr-based metal-organic framework (UiO-66(Zr)) composite catalyst, namely, Ce-BDC@HSiW@UiO-66 for the production of biodiesel through green fatty acid esterification. The obtained hybrids were characterized by various characterization technologies, including Fourier transform infrared, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N2 physisorption, X-ray photoelectron spectroscopy, and temperature-programmed desorption of NH3 (NH3-TPD) analysis. The characterization analyses showed that the hybrids have been successfully synthesized. Also, the volume and pore size of UiO-66(Zr) were changed by introducing HSiW@Ce-BDC, and the resulting Ce-BDC@HSiW@UiO-66 possessed the mesoporous structure and relatively high surface area. Simultaneously, the NH3-TPD analysis of Ce-BDC@HSiW@UiO-66 reveals that the acid strength was increased in comparison with HSiW@Ce-BDC. In addition, the composite Ce-BDC@HSiW@UiO-66 demonstrated high catalytic activity, and the oleic acid esterification gave 81.5% conversion at optimum conditions of 0.2 g catalysts, 1:30 oleic acid to methanol molar ratio at 130°C for 4 h. More interestingly, after six recycling cycles, the reduction in the conversion rate was only 4.6%, indicating that Ce-BDC@HSiW@UiO-66 has excellent reusability. Our study provides an effective approach to synthesize multifunctional hybrids for green biofuel production.

The developed MOF-derived ZrO2 supported silicotungstic acid nanoporous hybrids is a highly efficient catalyst in esterification.

MIL-125(Ti) metal–organic framework-derived nanoporous titanium dioxide–heteropoly acid (PW–TiO2) have been synthesized by a facile hydrothermal approach and subsequent calcination, and the PW–TiO2 catalysts were investigated using various characterization technologies including FTIR, XRD, SEM, TEM, N2-physisorption, and NH3-TPD. Further, we investigated the use of PW–TiO2 composites as heterogeneous acid catalysts for the catalytic esterification of oleic acid. Among all series of catalysts, the calcined PW–TiO2 at a temperature of 350°C showed excellent activity with a high conversion of 90.5% at 160°C for 4 h. More importantly, the catalyst could be simply separated via centrifugation and reused for six cycles and shows a relatively high conversion of 74.8%.

The impregnation of phosphotungstic acid (HPW) with porous cobalt-cerium oxide (HPW@CoCeO) has been prepared by pyrolysis of CoCe-MOF and used for the production of methyl oleate from oleic acid and methanol. FTIR, XRD, SEM, TEM, N2 adsorption/desorption, and NH3-TPD were characterized for the prepared composites. Simultaneously, the effects of reaction time, substrate molar ratio, temperature, and catalyst loading on catalytic activity were highlighted, and the conversion of 67.2% was reached after 4 h at 60°C. Importantly, HPW@CoCeO was reusabe and reused more than eight times, and the oleic acid conversion could be maintained at 61.8% without significant activity loss. Thus, the HPW@CoCeO composite could be used as acid catalysts for sustainable energy production.