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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%.

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]

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.

In this study, the bimetallic Ni-Zr MOF-derived nickel-zirconium oxide (Ni-Zr-O)-impregnated silicotungstic acid (HSiW) nanocomposite catalyst (HSiW@Ni-Zr-O) was prepared via a hydrothermal procedure followed by a pyrolysis treatment, and its structural, morphological, and surface components and oxidation states were characterized by using XRD, FTIR, TPD-NH3, SEM, TEM, N2 physisorption, and XPS analyses. Then, the nanocomposite catalysts were successfully applied to the esterification of oleic acid (OA) with methanol. According to its characteristics, the obtained HSiW@Ni-Zr-O-1 catalyst would generate larger pores, a higher acidity, and active interfaces at the calcining temperature of 300 °C. Therefore, HSiW@Ni-Zr-O-1 exhibits an excellent catalytic activity of 95.2% under optimal reaction conditions. Additionally, the catalyst can be reused with a good catalytic activity after nine cycles. This study highlights the opportunity of using bimetallic MOFs as precursors to the synthesis of highly nanoporous metal oxide, which supports the larger-industrial scale production of biofuels. [ABSTRACT FROM AUTHOR]

[Display omitted] • 12-tungstophosphoric acid (TPA) immobilized on Sn-based MOFs (Sn(II)-BDC) was successfully fabricated with water as a solvent. • The TPA/Sn(II)-BDC catalyst exhibits excellent catalytic activity and recyclability. • The highest conversion of oleic acid (91.7%) was achieved over TPA/Sn(II)-BDC. • Reaction kinetics were evaluated for oleic acid esterification. Facilitating energy resource deficiency and environmental contamination, this work focuses on sustainable biodiesel production through the esterification reactions of oleic acid (OA) with methanol. To address the reaction, a novel heterogeneous acid catalyst, 12-tungstophosphoric acid (TPA) immobilized on Sn-based MOFs (Sn(II)-BDC) was synthesized via a simple, green solvent, and easy-to-implement synthesis strategy for the first time, and applied effectively for esterification process of OA to produce biodiesel. The structure and composition of as-obtained catalyst have been verified using XRD, FTIR, N 2 physisorption, SEM, EDX, TG, Py-FTIR, TPD-NH 3 , and XPS techniques. The obtained TPA/Sn(II)-BDC catalyst was found to be the best with 60 wt% of TPA loading, which resulted in an OA conversion of 91.7 % at optimized conditions of 0.15 g catalyst loading and methanol to OA molar ratio of 20:1 at temperature of 120 °C in 4 h, and the excellent performance arises from available pores structure, large amounts of acidic sites, good stability and the synergistic catalytic effect of TPA and Sn(II)-BDC. Furthermore, the composite catalyst reusability has been studied for five cycles, and it exhibits an acceptable conversion. This research provides a green and large-scale synthesis route for the sustainable production of biofuels by constructing heteropolyacids/Sn-based MOFs synergistic catalysts. [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]

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. [ABSTRACT FROM AUTHOR]

In this study, the silver-exchanged heteropolyacids were prepared by a simple and environmentally friendly ion exchange method, were found to be active in the esterification of oleic acid with methanol to produce biodiesel. The catalysts were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) and scanning electron microscopy (SEM), separately. The effect of various factors was investigated to optimize the reaction conditions. The results showed that the oleic acid conversion can reach 91.3% after reacting for 3 h at 70°C, with oleic acid to methanol ratio of 1:10 and the amount of catalyst of 5 wt.%. Moreover, the catalyst could be easily separated from the reaction mixture and used repeatedly for five cycles with the oleic acid conversion over 50.1%, due to its relative stability. In particular, this catalyst can also catalyze other esterification of fatty acids with different chain length of carboxylic acid and high acid value non-edible oils, which may provide significant benefits for developing an environmentally benign and continuous process for synthesizing biodiesel in the future. [ABSTRACT FROM AUTHOR]