The effects of the metal incorporation into hydroxyapatites on the deactivation behavior of the solids were examined in the esterification of glycerol (EG) reaction. The introduction of Cu, Co, or Ni ions by ion exchange in calcium-deficient hydroxyapatites resulted in active catalysts for the EG reaction. The metal contents were varied from 2.0 to 17.0%, providing better performances at rather high metal contents. Part of metal species existed in the hydroxyapatite lattice structure and also as isolated Cu2+, Ni2+, and Co2+ entities on the surface, as shown by XPS and EPR. The effects of the reaction temperature, reaction time, and glycerol to acetic acid molar ratios were deeply investigated. The spent solids used in this study were characterized by XRD, FTIR, SEM-EDS, chemical analyses, EPR, and XPS. The Cu2+–OH acid pairs could promote a superior catalytic performance of Cu-containing hydroxyapatites due to the resistance of these solids against leaching of the active species, which is even better than those of Co and Ni-containing counterparts with high metal contents. Cu into hydroxyapatite had a good reusability and long-term utilization for five consecutive cycles of 24 h under a glycerol to acetic acid molar ratio of 0.25 at 80 °C, and longer reaction times provide triacetin formation. This was due to the fact that Cu was stabilized by interacting with Ca, PO4, and OH sites into the hydroxyapatite lattice, being highly active for the EG reaction. The results also revealed that isolated Cu2+ sites played an important role in enhancing the glycerol conversion, intrinsically due to the Cu-containing hydroxyapatites ability to avoid strong adsorption of glycerol oligomers on the catalytic sites.
Effects of the incorporation of Cr, Ni, Co, Ag, Al, Ni and Pt cations in titanate nanotubes (NTs) were examined on the NOx conversion. The structural and morphological characterizations evidenced that the ion-exchange reaction of Cr, Co, Ni and Al ions with the NTs produced catalysts with metals included in the interlayer regions of the trititanate NTs whereas an assembly of Ag and Pt nanoparticles were either on the nanotubes surface or inner diameters through an impregnation process. Understanding the role of the different metal cations intercalated or supported on the nanotubes, the optimal selective catalytic reduction of NOx by CO reaction (SCR) conditions was investigated by carrying out variations in the reaction temperature, SO2 and H2O poisoning and long-term stability runs. Pt nanoparticles on the NTs exhibited superior activity compared to the Cr, Co and Al intercalated in the nanotubes and even to the Ag and Ni counterparts. Resistance against SO2 poisoning was low on NiNT due to the trititanate phase transformation into TiO2 and also to sulfur deposits on Ni sites. However, the interaction between Pt2+ from PtOx and Ti4+ in the NTs favored the adsorption of both NOx and CO enhancing the catalytic performance.
A series of the Cr-containing erbium substituted yttrium iron garnet ferrites (ECYIG) was synthesized with distinct Cr amounts, herein referred to as Y3(Er0.02Fe5Cr1−x)O12, where x refers to Cr amounts from 0 to 0.05. The catalytic performance of the solids was investigated in ethylbenzene oxidation in the presence of hydrogen peroxide to assess the role of Cr and Er present in the YIG garnet lattice for fine chemistry compound production. Raman spectroscopy, HRTEM, EPR and FTIR revealed that the insertion of Er (at a fixed amount of 2%) in dodecahedral sites had a great impact on the catalytic activity of the garnets. Both Er3+ and Y3+ in the lattice simultaneously provided structural stability to the garnet structure in any harsh environment. XPS and EPR indicated that the Cr3+ ions replaced those of Fe3+ located in both octahedral and tetrahedral sites of the YIG garnets. The Cr3+ ions acted as electronic promoter to increase the oxidation rate of the Fe3+ active species responsible for activating the EB molecule. SEM-EDS demonstrated that the solids having Cr amounts lower than 4% experienced the most severe deactivation due to the Cr leaching and strong carbon species adsorption on the surface of the catalysts, which decreased their efficiency in the reaction.
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