Laser-power dependence effects on the structural stability of nanocomposite catalysts studied by Raman spectroscopy: On the structure-activity correlations in glycerol acetylation

• Published in: Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy Molecular and biomolecular spectroscopy, 2022-11, Vol.280, p.121526, Article 121526
• Main Authors: Gonçalves, Marcos Davi L., Assis, Pierre B.N., da Silva, Antonio N., Bertoldo, Gabriela M., Bezerra, Rita de Cassia F., Castro, Antonio Joel R., Oliveira, Alcineia C., Lang, Rossano, Saraiva, Gilberto D.
• Format: Article
• Language: English
• Subjects: Catalysts; Glycerol; Laser heating effects; Nanocomposite; Raman spectroscopy
• ISSN: 1386-1425
• DOI: 10.1016/j.saa.2022.121526

[Display omitted] •Laser induced local heating disorder with the sintering of CeMn, SnTi, and ZrMn nanocomposite catalysts.•High amounts of oxygen vacancy defects and stability over CeAl upon laser power heating.•Structure-activity correlations showed CeAl very active in glycerol acetylation.•Phase transformation and particle growths caused low catalytic performance of NiAl, SnTi, CeMn and ZrMn. Structural properties of binary CeAl, CeMn, NiAl, CeZr, SnTi and ZrMn nanocomposite oxide catalysts were monitored towards the Laser Raman spectroscopy investigations providing new insights to control catalytic applications upon temperature ranges at which the laser power was varied. The lattice vibrational properties were investigated by varying the incident laser power during Raman measurements from 0.017 mW to 4.0 mW. Structural changes in nanocomposites were achieved upon increasing laser power, which induced local heating disorder causing the sintering of CeMn, SnTi, and ZrMn nanocomposites. The laser-power dependence effects on the structural stability of CeAl, NiAl, and CeZr were observed with high amounts of oxygen vacancy defects over CeAl upon laser power heating. Both CeMn and ZrMn exhibited phase transitions from MnO2 to α-Mn2O3 being the use of the latter nanocomposites limited to work at 1.1 mW. The structure-activity correlations for the nanocomposite oxide catalysts were evaluated through the acetylation of glycerol with acetic acid reaction to produce valuable acetins. Remarkable shifts in the Raman bands wavenumbers and other spectral changes in the lattice mode were caused by laser-induced phenomena accounting for the undesired phase formation and particle growths, as well. This resulted in a low catalytic performance of the NiAl, SnTi, CeMn and ZrMn owing to the thermal effects. Contrary, CeAl and CeZr were more active for acetins products avoiding the phase transformations due to their structural stability at high temperatures, which in turn avoided leaching of the active Ce sites during the reaction.