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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.

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%.

Nickel salts of Keggin-type heteropolyacid on Zr(IV)-based metal-organic frameworks (UiO-66) has been synthesized via ion-exchange followed by a facile one-pot hydrothermal method. The synthesized catalysts underwent FT-IR, N2 adsorption-desorption, powder XRD, SEM and TEM analysis. The NiHSiW/UiO-66 catalyst was used as a new and effective solid acid in the catalytic transfer free fatty acid to biodiesel with an optimum conversion of 86.7%. The excellent activity of the NiHSiW/UiO-66 nanocatalyst was closely related to its high specific surface area, nano-sized catalyst, and the synergistic effects of NiHSiW salts and UiO-66 matrix. Importantly, a relatively stable catalytic performance was achieved for 8 repeated cycles. Finally, kinetics of the esterification reaction have been assumed to be of pseudo first order.

Development of an energy‐efficient and economical route is necessary for society to synthesize green biofuels. Herein, cobalt‐doped tungstophosphoric acid (Co‐HPW) is in‐situ impregnated in the Zr‐based metal–organic framework (MOF‐801) forming composite of Co‐HPW/MOF‐801. The chemical composition, morphology, and acidic sites of the Co‐HPW/MOF‐801 composite were analyzed through x‐ray diffractometer (XRD), Fourier transform infrared (FTIR), scanning electron microscope (SEM), energy‐dispersive x‐ray spectroscopy (EDS), thermogravimetric analysis (TG), N2 physisorption, ammonia temperature‐programmed desorption (NH3‐TPD), pyridine‐adsorbed infrared spectra (Py‐FTIR), and x‐ray photoelectron spectroscopy (XPS). The catalytic performance of the as‐synthesized catalyst was explored to catalyze esterification of lauric acid (LA) with methanol. The outcomes revealed that the Co‐HPW/MOF‐801 nanocatalyst achieved a high conversion of 86.3% under the optimized reaction condition (catalyst amount of 0.15 g, temperature of 100°C, time of 4 h, and methanol/LA molar ratio of 20:1). The excellent catalytical performance is mainly due to the large BET surface area, exposure of more active centers from available pore structure, and simultaneous possession of high Lewis and Brønsted acidity. Furthermore, the kinetic study revealed that the reaction process was kinetically controlled and the activation energy was found to be 42.1 kJ/mol. The results suggest that the synthesized Co‐HPW/MOF‐801 nanocatalyst is an environmental greenness, low cost, and suitable for easy scale‐up for the production of biofuels. [ABSTRACT FROM AUTHOR]

In the present study, phosphomolybdic acid (HPMo) supported on Cu-BTC Metal-organic frameworks (MOFs) were prepared and utilized as a solid acid catalyst. The structure of the synthesized materials was characterized by using powder XRD, FT-IR, N2 adsorption-desorption, SEM, TEM, TG, and NH3-TPD techniques. These results exposed that HPMo was successfully encapsulated in the Cu-BTC cage and the Keggin structure of HPMo was maintained in the composite catalyst. In addition, the catalytic activity and recovery properties of the HPMo/Cu-BTC catalyst for the esterification of oleic acid with methanol into biodiesel were evaluated. These results showed that the HPMo/Cu-BTC catalyst exhibited high conversion (93.7%) and excellent reusability due to its mesoporous structure, excellent acidic activity, high BET surface area, large pore volume, and good thermal stability. Meanwhile, the kinetic studies of the esterification reaction revealed that it follows pseudo-first-order kinetics with a low activation energy of 37.5 KJ/mol. More interestingly, it shows potential application for esterification of free fatty acids (FFAs) or pretreatment of low-cost feedstocks contain high FFAs content for the green production of biodiesel. [ABSTRACT FROM AUTHOR]