The studies of pyrolysis of caffeic acid (CA) and its surface complexes is important for the development of technologies of heterogeneous catalytic pyrolysis of plant- and wood- based renewable biomass components. In this work, the structure and thermal transformations of the surface complexes of CA on the surface of nanoceria were investigated using Fourier transform–infrared (FT–IR) spectroscopy, thermogravimetric analysis (TGA) and temperature-programmed desorption mass spectrometry (TPD MS). It was found that CA on the surface of cerium dioxide forms several types of complexes: bidentate carboxylates, monodentate carboxylates and complexes formed as a result of interaction with phenolic hydroxyl groups. This is due to the ability of nanosized cerium dioxide to generate basic hydroxyl groups that can deprotonate phenolic groups to form phenolates on the surface. The main pyrolysis products were identified. The possible ways of forming 3,4-dihydroxyphenylethylene, acetylene carboxylic acid, pyrocatechol and phenol from surface complexes of CA were suggested. It was established that on the nanoceria surface effectively occur the decarboxylation, decarbonylation, and dehydration reactions of the CA, which are the desirable processes in biomass conversion technologies.
1 October 2015 in Polymer Degradation and Stability
Lignin processing products have an extensive using range. Because products properties depend on lignin precursor quality it was interesting to study lignin isolated from rice husk being a large tonnage waste of rice production and its structural transformations during carbonization. Lignin isolated by the thermal hydrolysis method with H2SO4 1 wt % solution and its carbonized products prepared under different carbonization conditions were characterized using elemental analysis, IR, TPD-MS, XRD, TEM, and EPR. It was shown lignin degradation takes place over the wide (220–520 °C) temperature range. Silica presenting in lignin affects the thermal destruction of this polymer. Due to the strong chemical bond with phenolic hydroxylic group it decreases an evaporation of volatile compounds and as a result increases the temperature range of the lignin degradation. Rice husk hydrolytic lignin transformations during carbonization occur with generation of free radicals. Their concentration is decreased after condensation of aromatic rings with carbon polycycles formation, i.e., the graphite-like structure. Quantity and X-ray diffraction characteristics of the graphite-like phase depend on carbonization conditions. Morphology of the lignin-based carbonized products is represented by carbon fibers, carbon and silica nanoparticles, and together with another structure characteristics provides prospective performance properties of lignin-based end products.