Hydrodeoxygenation of anisole over SBA-15-supported Ni, Pd, and Pt mono- and bimetallic catalysts: effect of the metal's nature on catalytic activity and selectivity.

Monometallic Ni, Pd and Pt and bimetallic catalysts formed by combinations of the above metals supported on SBA-15 silica were synthesized, characterized and tested in the hydrodeoxygenation reaction of anisole. The objective of the work was to detect the effect of the nature of metals on the activity of the catalysts at different steps of anisole hydrodeoxygenation: hydrogenation of the aromatic ring of anisole and C-O bond cleavage in the intermediate cyclohexyl methyl ether. The support and the catalysts were characterized by N2 physisorption, X-ray diffraction, UV-vis diffuse reflectance spectroscopy, temperature-programmed reduction, scanning electron microscopy-energy dispersive X-ray spectroscopy, transmission electron microscopy and HAADF-STEM. The catalytic activity tests were carried out in a batch reactor at 280 °C and 7.3 MPa pressure. The activity results show that the NiPd/SBA-15 catalyst had the greatest ability for hydrogenation of the aromatic ring of anisole, while its NiPt/SBA-15 analog resulted in better activity for C-O bond hydrogenolysis. The bimetallic NiPt/SBA-15 catalyst showed the best catalytic performance in the HDO of anisole ascribed to the formation of a Ni-Pt alloy. On the other hand, the combination of Pd and Pt metals in the PdPt/SBA-15 catalyst resulted in the formation of bimetallic particles with Pd-rich and Pt-rich domains, showing high selectivity for the formation of the cyclohexyl methyl ether, which can be useful for the hydrogenation of aromatic rings in O-containing reactants with the formation of saturated O-containing products. According to the characterization results (HAADF-STEM), the different catalytic behavior of NiPd/SBA-15, NiPt/SBA-15, and PdPt/SBA-15 catalysts could be attributed to different characteristics of the bimetallic active phases in them.

Boosting the Hydrodeoxygenation Activity and Selectivity of Ni/(M)-SBA-15 Catalysts by Chemical Alteration of the Support.

The influence of the acid sites in the hydrodeoxygenation of anisole performed over Ni catalysts supported on SBA-15 modified with metal oxides (Ni/M-SBA-15, M = Ti, Zr, Al, or Nb) was demonstrated. Catalysts were characterized by SEM-EDX, nitrogen physisorption, XRD, UV-visible DRS, TPR, TPD of ammonia, IR-Py, O2 chemisorption, and high-resolution transmission electron microscopy. The mesoporous structure and the hexagonal arrangement of the supports were maintained in the catalysts. Ni catalysts supported on modified M-SBA-15 exhibited a higher metal-support interaction, an increase in the acidity and, as a consequence, improved selectivity to cyclohexane. The deoxygenation reaction rate constants increased as Ni/SBA-15 < Ni/Ti-SBA-15 < Ni/Nb-SBA-15 < Ni/Zr-SBA-15 < Ni/Al-SBA-15, which is attributed to the increase in the amount and strength of acid sites, especially of the Brønsted ones, which promotes the cleavage of the C-O bond. It is also important to keep the metal/acid sites together to obtain high activity and selectivity to hydrodeoxygenated products.