A multi-method study of the transformation of the carbonaceous skeleton of a polymer-based nanoporous carbon along the activation pathway

The change in the carbonaceous skeleton of nanoporous carbons during their activation has received limited attention, unlike its counterpart process in the presence of an inert atmosphere. Here we adopt a multi-method approach to elucidate this change in a poly(furfuryl alcohol)-derived carbon activated using cyclic application of oxygen saturation at 250 °C before its removal (with carbon) at 800 °C in argon. The methods used include helium pycnometry, synchrotron-based X-ray diffraction (XRD) and associated radial distribution function (RDF) analysis, transmission electron microscopy (TEM) and, uniquely, electron energy-loss spectroscopy spectrum-imaging (EELS-SI), electron nanodiffraction and fluctuation electron microscopy (FEM). Helium pycnometry indicates the solid skeleton of the carbon densifies during activation from 78% to 93% of graphite. RDF analysis, EELS-SI, and FEM all suggest this densification comes through an in-plane growth of sp2 carbon out to the medium range without commensurate increase in order normal to the plane. This process could be termed ‘graphenization’. The exact way in which this process occurs is not clear, but TEM images of the carbon before and after activation suggest it may come through removal of the more reactive carbon, breaking constraining cross-links and creating space that allows the remaining carbon material to migrate in an annealing-like process.

Raman spectroscopy study of the transformation of the carbonaceous skeleton of a polymer-based nanoporous carbon along the thermal annealing pathway

We report a multi-wavelength Raman spectroscopy study of the structural changes along the thermal annealing pathway of a poly(furfuryl alcohol) (PFA) derived nanoporous carbon (NPC). The Raman spectra were deconvoluted utilizing G, D, D′, A and TPA bands. The appropriateness of these deconvolutions was confirmed via recovery of the correct dispersive behaviours of these bands. It is proposed that the ID/IG ratio is composed of two parts: one associated with the extent of graphitic crystallites (the Tuinstra–Koenig relationship), and a second related to the inter-defect distance. This model was used to successfully determine the variation of the in-plane size and intra-plane defect density along the annealing pathway. It is proposed that the NPC skeleton evolves along the annealing pathway in two stages: below 1600 °C it was dominated by a reduction of in-plane defects with a minor crystallite growth, and above this temperature growth of the crystallites accelerates as the in-plane defect density approaches zero. A significant amount of transpolyacetylene (TPA)-like structures was found to be remaining even at 2400 °C. These may be responsible for resistance to further graphitization of the PFA-based carbon at higher temperatures.