It has been verified that UiO-66(Zr) is an effective heterogeneous catalyst for the production of biodiesel. The construction of multimetal sites in the structure of UiO-66(Zr) can be a promising way to enhance the catalytic performance of UiO-66(Zr). In this contribution, UiO-66(Zr) with tin sites is simply fabricated under solvent-free conditions. The results from XRD, EDX, and XPS analyses indicate that tin species have been introduced into the structure of UiO-66(Zr). The nitrogen sorption data show that UiO-66(Zr/Sn)-5-130-24 obtained under optimized synthesis conditions maintains a large BET specific surface area (1170 m2/g) and pore volume (0.84 cm3/g). The NH3-TPD results reveal that UiO-66(Zr/Sn)-5-130-24 possesses more acid sites than UiO-66(Zr) probably because the introduction of tin species brought about the missing of linkers in the structure of UiO-66(Zr). As a consequence, UiO-66(Zr/Sn)-5-130-24 exhibits higher catalytic efficiency with an oleic acid conversion of 98.8% than UiO-66(Zr) (oleic acid conversion of 86.2%) at 333 K in the esterification reaction of oleic acid with methanol to obtain biodiesel. Furthermore, the reusability test demonstrates that such a catalyst can be readily recycled and reused.
UiO-66(Zr) has been demonstrated to be an efficient heterogeneous catalyst in the esterification of oleic acid and methanol for biodiesel production. For the development of multi-functional sites in the structure of UiO-66(Zr), direct synthesis of UiO-66(Zr) with extra metal centers is a challenge. Based on our previous work of solvent-free synthesis, tin-doped UiO-66(Zr) was prepared under solvent-free conditions. The produced materials were analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD), N2 sorption technique, Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD) analysis of NH3. The results indicate that UiO-66(Zr/Sn)-green with bimetal centers exhibits superior catalytic performance in the esterification of oleic acid. Additionally, the influence of tin integration on the structure and reactivity of UiO-66(Zr) significantly accelerates the esterification process at room temperature. Such catalyst could easily be recycled and reused.
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