dc.description.abstract
The transformation of wood into advanced carbon materials relies on the partial preservation
of its hierarchical structure after thermal treatments. Unlike isotropic materials, wood exhibits
inherent anisotropy due to the alignment of cellulose fibrils along the tree’s growth direction
within its lignocellulosic matrix. In this study, a pre-oxidation step was introduced before
pyrolysis to investigate the effects of structural decomposition at five different temperatures:
250°C, 275°C, 287°C, 300°C and 325°C. These temperatures remain below the threshold for
complete cellulose and lignin decomposition, selectively modifying the matrix by targeting
hemicellulose, while aiming to preserve the alignment of cellulose fibers through subsequent
pyrolysis at 800°C under two different heating rates (7°C/min, 1°C/min) and atmospheres
(Nitrogen, Vacuum), and finally activation at 800°C with CO2
, ultimately leading to the
formation nanoporous carbons with some anisotropy.
To assess structural modifications, Wide-Angle X-ray Diffraction (WAXD) was used to study the
crystallography of cellulose by their intensity curves, focused on the <110>, <11̅0> and <020>
planes through all thermal steps. For the pyrolized samples, crystallite sizes from turbostratic
nanocarbons arrangement were calculated for the in-plane (La) and out-of-plane (Lc)
directions, according to <100> and <002> planes respectively. From the azimuthal intensity
distribution of pyrolized samples a parameter 𝜂� was calculated as a degree of preferred
orientation. Beyond WAXD, Small-Angle X-ray Scattering (SAXS) elucidated the density phase
contrast difference between cellulose and lignocellulosic matrix for pre-oxidized samples, and
details of pore structure for the pyrolized samples. Gas sorption measurements (N2 at 77k and
CO2 at 273k) were conducted to investigate the specific pore volume (SPV), specific surface
area (SSA) and pore size distribution (PSD) of the pyrolized and activated samples.
As a main important outcome, samples that underwent partial oxidation at 287°C showed
decomposition of hemicellulose while mostly preserving the crystalline cellulose fiber
structure, indicating a controllable method to partially decompose the lignocellulosic matrix.
Moreover, 287°C pre-oxidated wood followed by pyrolysis at 800°C with 1°C/min heating rate
under vacuum demonstrated enhanced development of pore structure as well as the highest
degree of preferred orientation with around 12% of the carbon being preferentially oriented
along the tree’s growth direction. Final activation at 800°C with CO2
indicated pore structure
development and high material yield for same pre-oxidated temperature at 287°C followed
by pyrolysis at 800°C with 1°C/min heating rate. This highlights the potential to preserve
anisotropic features to some extent after thermal treatments, suggesting pathways for
tailoring wood nanocarbons for advanced functional applications.
